2,4,5-Trisubstituted phenylketoenols

ABSTRACT

The invention relates to new phenyl-substituted cyclic ketoenols of the formula (I) 
                 
 
in which
         Het represents one of the groups 
                 
 
wherein A, B, D, G, X, Y and Z have the meaning given in the description, several processes and intermediate products for their preparation and their use as pest control agents and herbicides.

This application is a divisional application of U.S. Ser. No.09/496,616, filed on 2 Feb. 2000, now U.S. Pat. No. 6,511,942 which is adivisional of U.S. Ser. No. 08/983,028, filed on 22 Dec. 1997, now U.S.Pat. No. 6,110,872, which is a 371 of PCT/EP96/02608, filed on 17 Jun.1996.

The invention relates to new phenyl-substituted cyclic ketoenols,several processes and intermediate products for their preparation andtheir use as pest control agents and herbicides.

It has already been disclosed that certain phenyl-substituted cyclicketoenols are active as insecticides, acaricides and/or herbicides.

Pharmaceutical properties have already been described for3-acyl-pyrrolidine-2,4-diones (S. Suzuki et al. Chem. Pharm. Bull. 151120 (1967)). Furthermore, N-phenylpyrrolidine-2,4-diones have beensynthesized by R. Schmierer and H. Mildenberger (Liebigs Ann. Chem.1985, 1095). No biological activity has been described for thesecompounds.

EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of similarstructure (3-aryl-pyrrolidine-2,4-diones), of which, however, noherbicidal, insecticidal or acaricidal action has been disclosed. Knowncompounds which have a herbicidal, insecticidal or acaricidal action areunsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives(EP-A-355 599 and EP-A-415 211) and substituted monocyclic3-aryl-pyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442077).

Compounds which are furthermore known are polycyclic3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073) and1H-arylpyrrolidine-dione derivatives (EP-A-456 063, EP-A-521 334,EP-A-596 298, EP-A-613 884, EP-A-613 885, DE 44 40 594, WO 94/01 997 andWO 95/01 358).

It is known that certain substituted Δ³-dihydrofuran-2-one derivativeshave herbicidal properties (cf. DE-A-4 014 420). The synthesis of thetetronic acid derivatives used as starting compounds (such as, forexample,3-(2-methyl-phenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ³-dihydrofuran-2-one)is likewise described in DE-A-4 014 420. Compounds of similar structure,without an insecticidal and/or acaricidal activity being mentioned, areknown from the publication Campbell et al., J. Chem. Soc., Perkin Trans.1, 1985, (8) 1567-76. 3-Aryl-Δ³-dihydrofuranone derivatives havingherbicidal, acaricidal and insecticidal properties are furthermore knownfrom EP-A-528 156, EP-A 0 647 637 and WO 95/26345.

Certain phenyl-pyrone derivatives which are unsubstituted in the phenylring have already been disclosed (cf. A. M. Chirazi, T. Kappe and E.Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K.Heidenbluth, Chem. Ber. 91, 2849), no possible usefulness of thesecompounds as pest control agents being mentioned. Phenyl-pyronederivatives which are substituted in the phenyl ring and haveherbicidal, acaricidal and insecticidal properties are described inEP-A-588 137.

Certain 5-phenyl-1,3-thiazine derivatives which are unsubstituted in thephenyl ring have already been disclosed (cf E. Ziegler and E. Steiner,Monatsh. 95, 147 (1964), R. Ketcham, T. Kappe and E. Ziegler, J.Heterocycl. Chem. 10, 223 (1973)), no possible use as pest controlagents being mentioned for these compounds. 5-Phenyl-1,3-thiazinederivatives which are substituted in the phenyl ring and have aherbicidal, acaricidal and insecticidal action are described in WO 94/14785.

However, the acaricidal and insecticidal activity and/or range of actionand the plant tolerance of these compounds, in particular with respectto crop plants, is not always adequate.

New compounds of the formula (I)

in which

-   -   X represents halogen, alkyl, alkenyl, alkinyl, alkoxy,        halogenoalkyl, halogenoalkoxy, cyano or nitro,    -   Y represents hydrogen, halogen, alkyl, alkoxy, halogenoalkyl,        halogenoalkoxy, cyano or nitro,    -   Z represents halogen, alkyl, alkoxy, halogenoalkyl,        halogenoalkoxy, hydroxyl, cyano, nitro or in each case        optionally substituted phenoxy, phenylthio, 5- to 6-membered        hetaryloxy, 5- to 6-membered hetarylthio, phenylalkyloxy or        phenylalkylthio or    -   Y and Z, together with the carbon atom to which they are bonded,        represent a cyclic radical which is optionally substituted and        optionally interrupted by heteroatoms, wherein X has one of the        abovementioned meanings,    -   Het represents one of the groups        -   wherein        -   A represents hydrogen, or represents alkyl, alkenyl,            alkoxyalkyl, polyalkoxyalkyl or alkylthioalkyl which are in            each case optionally substituted by halogen, or represents            in each case saturated or unsaturated and optionally            substituted cycloalkyl or heterocyclyl, or represents aryl,            arylalkyl or hetaryl which are in each case optionally            substituted by halogen, alkyl, halogenoalkyl, alkoxy,            halogenoalkoxy, cyano or nitro,        -   B represents hydrogen, alkyl or alkoxyalkyl, or        -   A and B, together with the carbon atom to which they are            bonded, represent a saturated or unsaturated, optionally            substituted carbocyclic or heterocyclic radical,    -   D represents hydrogen, or represents an optionally substituted        radical from the series consisting of alkyl, alkenyl, alkinyl,        alkoxyalkyl, polyalkoxyalkyl, alkylthioalkyl, saturated or        unsaturated cycloalkyl, saturated or unsaturated heterocyclyl,        arylalkyl, aryl, hetarylalkyl or hetaryl, or    -   A and D, together with the atoms to which they are bonded,        represent a carbocyclic or heterocyclic radical which is in each        case optionally substituted,    -   G represents hydrogen (a), or represents one of the groups        -   wherein        -   E represents one metal ion equivalent or an ammonium ion,        -   L represents oxygen or sulphur,        -   M represents oxygen or sulphur,    -   R¹ represents alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or        polyalkoxyalkyl which are in each case optionally substituted by        halogen, or represents cycloalkyl or heterocyclyl which are in        each case optionally substituted by halogen, alkyl or alkoxy, or        represents in each case optionally substituted phenyl,        phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,    -   R² represents alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl        which are in each case optionally substituted by halogen, or        represents in each case optionally substituted cycloalkyl,        phenyl or benzyl,    -   R³, R⁴ and R⁵ independently of one another represent alkyl,        alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or        cycloalkylthio which are in each case optionally substituted by        halogen, or represent in each case optionally substituted        phenyl, phenoxy or phenylthio, and    -   R⁶ and R⁷ independently of one another represent hydrogen, or        represent alkyl, cycloalkyl, alkenyl, alkoxy or alkoxyalkyl        which are in each case optionally substituted by halogen, or        represent in each case optionally substituted phenyl or benzyl,        or, together with the N atom to which they are bonded, form a        cyclic radical which optionally contains oxygen or sulphur and        is optionally substituted,        have now been found.

The compounds of the formula (I) can be in the form of geometric and/oroptical isomers or isomer mixtures of varying composition, alsodepending on the nature of the substituents, and these can optionally beseparated in the customary manner. The present invention relates both tothe pure isomers and to the isomer mixtures, their preparation and useand compositions comprising them. For simplicity, however, reference isalways made below to compounds of the formula (I), although this meansboth the pure compounds and, where appropriate, also mixtures withdifferent contents of isomeric compounds.

Incorporating the meanings (1) to (5) of the group Het, the followingmain structures (I-1) to (I-5) result:

wherein

-   -   A, B, D, G, X, Y and Z have the abovementioned meaning.

Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g)of the group G, the following main structures (I-1-a) to (I-1-g) resultif Het represents the group (1)

wherein

-   -   A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the        abovementioned meanings.

Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g)of the group G, the following main structures (I-2-a) to (I-2-g) resultif Het represents the group (2)

wherein

-   -   A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the        abovementioned meaning.

Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g)of the group G, the following main structures (I-3-a) to (I-3-g) resultif Het represents the group (3)

-   -   wherein    -   A, B, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the        abovementioned meaning.

The compounds of the formula (I-4) can be present in the two isomericforms of the formulae (I-4)_(a) and (I-4)_(b), depending on the positionof the substituent G

which is illustrated by the broken line in the formula (I-4).

The compounds of the formulae (I-4)_(a) and (I-4)_(b) can be presentboth in the form of mixtures and in the form of their pure isomers.Mixtures of the compounds of the formulae (I-4)_(a) and (I-4)_(b) can beseparated, where appropriate, by physical methods in a manner known perse, for example by chromatographic methods.

For reasons of better clarity, in each case only one of the possibleisomers is mentioned below. This does not mean that the compounds cannotbe present, where appropriate, in the form of the isomer mixtures or inthe other particular isomeric form.

Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g)of the group G, the following main structures (I-4-a) to (I-4-g) resultif Het represents the group (4)

-   -   wherein    -   A, D, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the        abovementioned meanings.

Incorporating the various meanings (a), (b), (c), (d), (e), (f) and (g)of the group G, the following main structures (I-5-a) to (I-5-g) resultif Het represents the group (5)

wherein

-   -   A, E, L, M, X, Y, Z, R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ have the        abovementioned meanings.

It has furthermore been found that the new compounds of the formula (I)are obtained by one of the processes described below:

-   -   (A) compounds of the formula (I-1-a)        -   in which        -   A, B, X, Y and Z have the abovementioned meanings,        -   are obtained when        -   compounds of the formula (II)        -   in which        -   A, B, X, Y and Z have the abovementioned meanings and        -   R⁸ represents alkyl (preferably C₁-C₆-alkyl)        -   are subjected to an intramolecular condensation reaction in            the presence of a diluent and in the presence of a base.    -   (B) It has furthermore been found that compounds of the formula        (I-2-a)    -    in which        -   A, B, X, Y and Z have the abovementioned meanings,        -   are obtained when        -   compounds of the formula (III)        -   in which        -   A, B, X, Y, Z and R⁸ have the abovementioned meanings,        -   are subjected to an intramolecular condensation reaction in            the presence of a diluent and in the presence of a base.    -   (C) It has furthermore been found that compounds of the formula        (I-3-a)        -   in which        -   A, B, X, Y and Z have the abovementioned meanings,        -   are obtained when        -   compounds of the formula (IV)        -   in which        -   A, B, X, Y, Z and R⁸ have the abovementioned meanings and        -   W represents hydrogen, halogen, alkyl (preferably            C₁-C₆-alkyl) or alkoxy (preferably C₁-C₈-alkoxy),        -   are subjected to intramolecular cyclization, if appropriate            in the presence of a diluent and in the presence of an acid.    -   (D) It has furthermore been found that compounds of the formula        (I-4-a)        -   in which        -   A, D, X, Y and Z have the abovementioned meanings,        -   are obtained when        -   compounds of the formula (V)        -   in which        -   A and D have the abovementioned meanings,        -   or silylenol ethers thereof of the formula (Va)        -   in which        -   A and D have the abovementioned meaning and        -   R^(8′) represents alkyl (preferably methyl),        -   are reacted with compounds of the formula (VI)        -   in which        -   X, Y and Z have the abovementioned meanings and        -   Hal represents halogen (preferably chlorine or bromine),        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid acceptor.    -   (E) It has furthermore been found that the compounds of the        formula (I-5-a)        -   in which        -   A, X, Y and Z have the abovementioned meanings,        -   are obtained when compounds of the formula (VII)        -   in which        -   A has the abovementioned meaning,        -   are reacted with compounds of the formula (VI)        -   in which        -   Hal, X, Y and Z have the abovementioned meanings,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid acceptor.            It has furthermore been found    -   (F) that the compounds of the formulae (I-1-b) to (I-5-b) shown        above, in which A, B, D, R¹, X, Y and Z have the abovementioned        meanings, are obtained when compounds of the formulae (I-1-a) to        (I-5-a) shown above, in which A, B, D, X, Y and Z have the        abovementioned meanings, are reacted    -   α) with acid halides of the formula (VIII)        -   in which        -   R¹ has the abovementioned meaning and        -   Hal represents halogen (in particular chlorine or bromine),            or    -   β) with carboxylic acid anhydrides of the formula (IX)        R¹—CO—O—CO—R¹  (IX)        -   in which        -   R¹ has the abovementioned meaning,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid-binding agent;    -   (G) that the compounds of the formulae (I-1-c) to (I-5-c) shown        above, in which A, B, D, R², M, X, Y and Z have the        abovementioned meanings and L represents oxygen, are obtained        when compounds of the formulae (I-1-a) to (I-5-a) shown above,        in which A, B, D, X, Y and Z have the abovementioned meanings,        in each case are reacted        -   with chloroformic acid esters or chloroformic acid            thioesters of the formula (X)            R²—M—CO—Cl  (X)        -   in which        -   R² and M have the abovementioned meanings,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid-binding agent;    -   (H) that compounds of the formulae (I-1-c) to (I-5-c) shown        above, in which A, B, D, R², M, X, Y and Z have the        abovementioned meanings and L represents sulphur, are obtained        when compounds of the formulae (I-1-a) to (I-5-a) shown above,        in which A, B, D, X, Y and Z have the abovementioned meanings,        in each case    -   α) are reacted with chloromonothioformic acid esters or        chlorodithioformic acid esters of the formula (XI)        -   in which        -   M and R² have the abovementioned meanings,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid-binding agent, or    -   β) are reacted with carbon disulphide and then with compounds of        the formula (XII)        R²—Hal  (XII)        -   in which        -   R² has the abovementioned meaning and        -   Hal represents chlorine, bromine or iodine,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of a base,    -   (I) that compounds of the formulae (I-1-d) to (I-5-d) shown        above, in which A, B, D, R³, X, Y and Z have the abovementioned        meanings, are obtained when compounds of the formulae (I-1-a) to        (I-5-a) shown above, in which A, B, D, X, Y and Z have the        abovementioned meanings, in each case        -   are reacted with sulphonic acid chlorides of the formula            (XIII)            R³—SO₂—Cl  (XIII)        -   in which        -   R³ has the abovementioned meaning,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid-binding agent,    -   (J) that compounds of the formulae (I-1-e) to (I-5-e) shown        above, in which A, B, D, L, R⁴, R⁵, X, Y and Z have the        abovementioned meanings, are obtained when compounds of the        formulae (I-1-a) to (I-4-a) shown above, in which A, B, D, X, Y        and Z have the abovementioned meanings, in each case are reacted        -   with phosphorus compounds of the formula (XIV)        -   in which        -   L, R⁴ and R⁵ have the abovementioned meanings and        -   Hal represents halogen (in particular chlorine or bromine),        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid-binding agent,    -   (K) that compounds of the formulae (I-1-f) to (I-5-f) shown        above, in which A, B, D, E, X, Y and Z have the abovementioned        meanings, are obtained when compounds of the formulae (I-1-a) to        (I-5-a), in which A, B, D, X, Y and Z have the abovementioned        meanings, in each case are reacted        -   with metal compounds or amines of the formulae (XV) or (XVI)            Me(OR¹⁰)_(t)  (XV)        -   in which        -   Me represents a mono- or divalent metal (preferably an            alkali metal or alkaline earth metal, such as lithium,            sodium, potassium, magnesium or calcium),        -   t represents the number 1 or 2 and        -   R¹⁰, R¹¹ and R¹² independently of one another represent            hydrogen or alkyl (preferably C₁-C₈-alkyl),        -   if appropriate in the presence of a diluent,    -   (L) that compounds of the formulae (I-1-g) to (I-5-g) shown        above, in which A, B, D, L, R⁶, R⁷, X, Y and Z have the        abovementioned meanings, are obtained when compounds of the        formulae (I-1-a) to (I-5-a) shown above, in which A, B, D, X, Y        and Z have the abovementioned meanings, in each case    -   α) are reacted with isocyanates or isothiocyanates of the        formula (XVII)        R⁶—N═C═L  (XVII)        -   in which        -   R⁶ and L have the abovementioned meanings,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of a catalyst, or    -   β) are reacted with carbamic acid chlorides or thiocarbamic acid        chlorides of the formula (XVIII)        -   in which        -   L, R⁶ and R⁷ have the abovementioned meanings,        -   if appropriate in the presence of a diluent and if            appropriate in the presence of an acid-binding agent.

It has furthermore been found that the new compounds of the formula (I)have a very good activity as pest control agents, preferably asinsecticides, acaricides and herbicides, and furthermore have a verygood plant tolerance, in particular with respect to crop plants.

Formula (I) provides a general definition of the compounds according tothe invention. Preferred substituents and ranges of the radicals shownin the formulae mentioned above and below are explained below:

-   -   X preferably represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,        C₂-C₆-alkinyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,        C₁-C₄-halogenoalkoxy, cyano or nitro,    -   Y preferably represents hydrogen, halogen, C₁-C₆-alkyl,        C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano        or nitro,    -   Z preferably represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, hydroxyl, cyano or        nitro, or phenoxy, phenylthio, thiazolyloxy, pyridinyloxy,        pyrimidyloxy, pyrazolyloxy, phenyl-C₁-C₄-alkyloxy or        phenyl-C₁-C₄-alkylthio which are in each case optionally        substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano, or    -   Y and Z, together preferably represent C₃-C₄-alkanediyl or        C₃-C₄-alkenediyl which are optionally substituted by halogen,        C₁-C₆-alkyl, C₁-C₆-alkoxy or C₁-C₄-halogenoalkyl and in which        one to three members can optionally be replaced, independently        of one another, by oxygen, sulphur, nitrogen or a carbonyl        group, X having one of the abovementioned meanings.    -   Het preferably represents one of the groups    -   A preferably represents hydrogen, or represents C₁-C₁₂-alkyl,        C₂-C₈-alkenyl, C₁-C₁₀-alkoxy-C₁-C₈-alkyl,        poly-C₁-C₈-alkoxy-C₁-C₈-alkyl or C₁-C₁₀-alkylthio-C₁-C₆-alkyl        which are in each case optionally substituted by halogen, or        represents C₃-C₈-cycloalkyl which is optionally substituted by        halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy and in which one or two        methylene groups are optionally replaced by oxygen and/or        sulphur, or represents phenyl, naphthyl, phenyl-C₁-C₆-alkyl,        naphthyl-C₁-C₆-alkyl or hetaryl having 5 or 6 ring atoms and one        to three heteroatoms from the series consisting of oxygen,        sulphur and nitrogen, which are in each case optionally        substituted by halogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl,        C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano or nitro.    -   B preferably represents hydrogen, C₁-C₁₂-alkyl or        C₁-C₈-alkoxy-C₁-C₆-alkyl or    -   A, B and the carbon atom to which they are bonded preferably        represent C₃-C₁₀-cycloalkyl or C₅-C₁₀-cycloalkenyl, wherein one        methylene group is optionally replaced by oxygen or sulphur and        which are optionally substituted by C₁-C₈-alkyl,        C₃-C₁₀-cycloalkyl, C₁-C₈-halogenoalkyl, C₁-C₈-alkoxy,        C₁-C₈-alkylthio, halogen or phenyl, or    -   A, B and the carbon atom to which they are bonded preferably        represent C₅-C₆-cycloalkyl which is substituted by an        alkylenediyl group which optionally contains one or two oxygen        and/or sulphur atoms or by an alkylenedioxyl group or by an        alkylenedithioyl group, this substituent forming a further five-        to eight-membered ring with the carbon atom to which it is        bonded, or    -   A, B and the carbon atom to which they are bonded preferably        represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl in which two        substituents, together with the carbon atom to which they are        bonded, represent C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or        C₄-C₆-alkanedienediyl which are in each case optionally        substituted by C₁-C₆-alkyl, C₁-C₆-alkoxy or halogen and wherein        in each case one methylene group is optionally replaced by        oxygen or sulphur.    -   D preferably represents hydrogen, or represents C₁-C₁₂-alkyl,        C₃-C₈-alkenyl, C₃-C₈-alkinyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl,        poly-C₁-C₈-alkoxy-C₂-C₈-alkyl or C₁-C₁₀-alkylthio-C₂-C₈-alkyl        which are in each case optionally substituted by halogen, or        represents C₃-C₈-cycloalkyl which is optionally substituted by        halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkyl and in        which one or two methylene groups which are not directly        adjacent are optionally replaced by oxygen and/or sulphur, or        represent phenyl, hetaryl having 5 to 6 ring atoms and one or        two heteroatoms from the series consisting of oxygen, sulphur        and nitrogen, phenyl-C₁-C₆-alkyl or hetaryl-C₁-C₆-alkyl having 5        to 6 ring atoms and one or two heteroatoms from the series        consisting of oxygen, sulphur and nitrogen, which are in each        case optionally substituted by halogen, C₁-C₆-alkyl,        C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano        or nitro, or    -   A and D together preferably represent a C₃-C₆-alkanediyl,        C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl group in which in each        case one methylene group is optionally replaced by oxygen or        sulphur and which are in each case optionally substituted by        halogen or C₁-C₁₀-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio,        C₃-C₇-cycloalkyl, phenyl or benzyloxy which are in each case        optionally substituted by halogen, or by a further        C₃-C₆-alkanediyl, C₃-C₆-alkenediyl or C₄-C₆-alkadienediyl group        which forms a fused-on ring and in which in each case one        methylene group is optionally replaced by oxygen or sulphur and        which are optionally substituted by C₁-C₆-alkyl, or    -   A and D together represent a C₃-C₆-alkanediyl or        C₃-C₆-alkenediyl group which in each case optionally contains        one of the following groups    -   G preferably represents hydrogen (a), or represents one of the        groups        -   in which        -   E represents one metal ion equivalent or an ammonium ion,        -   L represents oxygen or sulphur and        -   M represents oxygen or sulphur.    -   R¹ preferably represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,        C₁-C₈-alkoxy-C₁-C₈-alkyl, C₁-C₈-alkylthio-C₁-C₈-alkyl or        poly-C₁-C₈-alkoxy-C₁-C₈-alkyl which are in each case optionally        substituted by halogen, or represents C₃-C₈-cycloalkyl which is        optionally substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy        and in which one or two methylene groups are optionally replaced        by oxygen and/or sulphur,    -   or represents phenyl which is optionally substituted by halogen,        cyano, nitro, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl,        C₁-C₆-halogenoalkoxy, C₁-C₆-alkylthio or C₁-C₆-alkylsulphonyl,    -   or represents phenyl-C₁-C₆-alkyl which is optionally substituted        by halogen, nitro, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy,    -   or represents 5- or 6-membered hetaryl having one or two        heteroatoms from the series consisting of oxygen, sulphur and        nitrogen which is optionally substituted by halogen or        C₁-C₆-alkyl,    -   or represents phenoxy-C₁-C₆-alkyl which is optionally        substituted by halogen or C₁-C₆-alkyl or    -   represents 5- or 6-membered hetaryloxy-C₁-C₆-alkyl which has one        or two heteroatoms from the series consisting of oxygen, sulphur        and nitrogen and is optionally substituted by halogen, amino or        C₁-C₆-alkyl.    -   R² preferably represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,        C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl which        are in each case optionally substituted by halogen,        -   or represents C₃-C₈-cycloalkyl which is optionally            substituted by halogen, C₁-C₆-alkyl or C₁-C₆-alkoxy, or        -   represents phenyl or benzyl which are in each case            optionally substituted by halogen, cyano, nitro,            C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl or            C₁-C₆-halogenoalkoxy.    -   R³ preferably represents C₁-C₈-alkyl which is optionally        substituted by halogen, or phenyl or benzyl which are in each        case optionally substituted by halogen, C₁-C₆-alkyl,        C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano        or nitro.    -   R⁴ and R⁵ independently of one another preferably represent        C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino,        di-(C₁-C₈-alkyl)amino, C₁-C₈-alkylthio or C₃-C₈-alkenylthio        which are in each case optionally substituted by halogen, or        represent phenyl, phenoxy or phenylthio which are in each case        optionally substituted by halogen, nitro, cyano, C₁-C₄-alkoxy,        C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio, C₁-C₄-halogenoalkylthio,        C₁-C₄-alkyl or C₁-C₄-halogenoalkyl.    -   R⁶ and R⁷ independently of one another preferably represent        hydrogen, or represent C₁-C₈-alkyl, C₃-C₈-cycloalkyl,        C₁-C₈-alkoxy, C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₂-C₈-alkyl which        are in each case optionally substituted by halogen, or represent        phenyl or benzyl which are in each case optionally substituted        by halogen, C₁-C₈-alkyl, C₁-C₈-halogenoalkyl or C₁-C₈-alkoxy, or        together represent a C₃-C₆-alkylene radical which is optionally        substituted by C₁-C₆-alkyl and in which one methylene group is        optionally replaced by oxygen or sulphur.    -   R¹³ preferably represents hydrogen, or C₁-C₈-alkyl or        C₁-C₈-alkoxy which are in each case optionally substituted by        halogen, or represents C₃-C₈-cycloalkyl which is optionally        substituted by halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy and in which        one methylene group is optionally replaced by oxygen or sulphur,        or represents phenyl, phenyl-C₁-C₄-alkyl or phenyl-C₁-C₄-alkoxy        which are in each case optionally substituted by halogen,        C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,        C₁-C₄-halogenoalkoxy, nitro or cyano.    -   R¹⁴ preferably represents hydrogen or C₁-C₈-alkyl, or    -   R¹³ and R¹⁴ together preferably represent C₄-C₆-alkanediyl.    -   R¹⁵ and R¹⁶ are identical or different and preferably represent        C₁-C₆-alkyl, or    -   R¹⁵ and R¹⁶ together preferably represent a C₂-C₄-alkanediyl        radical which is optionally substituted by C₁-C₆-alkyl or by        phenyl which is optionally substituted by halogen, C₁-C₄-alkyl,        C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, nitro        or cyano.    -   R¹⁷ and R¹⁸ independently of one another preferably represent        hydrogen, or represent C₁-C₈-alkyl which is optionally        substituted by halogen, or represent phenyl which is optionally        substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,        C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano, or    -   R¹⁷ and R¹⁸, together with the carbon atom to which they are        bonded, represent C₅-C₇-cycloalkyl which is optionally        substituted by C₁-C₄-alkyl and in which one methylene group is        optionally replaced by oxygen or sulphur.    -   R¹⁹ and R²⁰ independently of one another preferably represent        C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₁-C₁₀-alkoxy, C₁-C₁₀-alkylamino,        C₃-C₁₀-alkenylamino, di-(C₁-C₁₀-alkyl)amino or        di-(C₃-C₁₀-alkenyl)amino.    -   X particularly preferably represents fluorine, chlorine,        bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,        C₁-C₂-halogenoalkoxy, cyano or nitro,    -   Y particularly preferably represents hydrogen, fluorine,        chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy, cyano or nitro,    -   Z particularly preferably represents fluorine, chlorine,        bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,        C₁-C₂-halogenoalkoxy, hydroxy, cyano or nitro, or phenoxy or        benzyloxy which are in each case optionally substituted by        fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy, nitro or cyano, or    -   Y and Z, together particularly preferably represent        C₃-C₄-alkanediyl or C₃-C₄-alkenediyl which are optionally        substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,        C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and in which one or two        members which are not directly adjacent can optionally be        replaced, independently of one another, by oxygen, sulphur or        nitrogen, X having one of the abovementioned meanings.    -   Het particularly preferably represents one of the groups    -   A particularly preferably represents hydrogen, or represents        C₁-C₁₀-alkyl, C₂-C₆-alkenyl, C₁-C₈-alkoxy-C₁-C₆-alkyl,        poly-C₁-C₆-alkoxy-C₁-C₆-alkyl or C₁-C₈-alkylthio-C₁-C₆-alkyl        which are in each case optionally substituted by fluorine or        chlorine, or represents C₃-C₇-cycloalkyl which is optionally        substituted by fluorine, chlorine, C₁-C₄-alkyl or C₁-C₄-alkoxy        and in which one or two methylene groups are optionally replaced        by oxygen and/or sulphur, or represents phenyl, furanyl,        pyridyl, imidazolyl, triazolyl, pyrazolyl, indolyl, thiazolyl,        thienyl or phenyl-C₁-C₄-alkyl which are in each case optionally        substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,        C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, cyano        or nitro.    -   B particularly preferably represents hydrogen, C₁-C₁₀-alkyl or        C₁-C₆-alkoxy-C₁-C₄-alkyl or    -   A, B and the carbon atom to which they are bonded particularly        preferably represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl,        wherein in each case one methylene group is optionally replaced        by oxygen or sulphur and which are optionally substituted by        C₁-C₆-alkyl, C₃-C₈-cycloalkyl, C₁-C₃-halogenoalkyl,        C₁-C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorine or phenyl, or    -   A, B and the carbon atom to which they are bonded particularly        preferably represent C₅-C₆-cycloalkyl which is substituted by an        alkylenediyl group which optionally contains one or two oxygen        or sulphur atoms or by an alkylenedioxyl group or by an        alkylenedithiol group, this substituent, together with the        carbon atom to which it is bonded, forming a further five- to        seven-membered ring, or    -   A, B and the carbon atom to which they are bonded particularly        preferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in        which two substituents, together with the carbon atom to which        they are bonded, represent C₃-C₅-alkanediyl, C₃-C₅-alkenediyl or        butadienediyl which are in each case optionally substituted by        C₁-C₄-alkyl, C₁-C₄-alkoxy, fluorine, chlorine or bromine,        wherein in each case one methylene group is optionally replaced        by oxygen or sulphur.    -   D particularly preferably represents hydrogen, or represents        C₁-C₁₀-alkyl, C₃-C₆-alkenyl, C₃-C₆-alkinyl,        C₁-C₈-alkoxy-C₂-C₆-alkyl, poly-C₁-C₆-alkoxy-C₂-C₆-alkyl or        C₁-C₈-alkylthio-C₂-C₆-alkyl which are in each case optionally        substituted by fluorine or chlorine, or represents        C₃-C₇-cycloalkyl which is optionally substituted by fluorine,        chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl and        in which one or two methylene groups which are not directly        adjacent are optionally replaced by oxygen and/or sulphur, or        represents phenyl, furanyl, imidazolyl, pyridyl, thiazolyl,        pyrazolyl, pyrimidyl, pyrrolyl, thienyl, triazolyl or        phenyl-C₁-C₄-alkyl which are in each case optionally substituted        by fluorine, chlorine, bromine, C₁-C₄-alkyl,        C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, cyano        or nitro, or    -   A and D together particularly preferably represent a        C₃-C₅-alkanediyl or C₃-C₅-alkenediyl group wherein in each case        one carbon atom is optionally replaced by oxygen or sulphur and        which are optionally substituted by fluorine, chlorine or by        C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl,        phenyl or benzyloxy which are in each case optionally        substituted by fluorine or chlorine, or        -   which in each case optionally contain one of the following            groups:    -   G particularly preferably represents hydrogen (a), or represents        one of the groups        -   in which        -   E represents one metal ion equivalent or an ammonium ion,        -   L represents oxygen or sulphur and        -   M represents oxygen or sulphur.    -   R¹ particularly preferably represents C₁-C₁₆-alkyl,        C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,        C₁-C₆-alkylthio-C₁-C₆-alkyl or poly-C₁-C₆-alkoxy-C₁-C₆-alkyl        which are in each case optionally substituted by fluorine or        chlorine, or represents C₃-C₇-cycloalkyl which is optionally        substituted by fluorine, chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy        and in which one or two methylene groups are optionally replaced        by oxygen and/or sulphur,        -   or represents phenyl which is optionally substituted by            fluorine, chlorine, bromine, cyano, nitro, C₁-C₄-alkyl,            C₁-C₄-alkoxy, C₁-C₃-halogenoalkyl, C₁-C₃-halogenoalkoxy,            C₁-C₄-alkylthio or C₁-C₄-alkylsulphonyl,        -   or represents phenyl-C₁-C₄-alkyl which is optionally            substituted by fluorine, chlorine, bromine, C₁-C₄-alkyl,            C₁-C₄-alkoxy, C₁-C₃-halogenoalkyl or C₁-C₃-halogenoalkoxy,        -   or represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl,            furanyl or thienyl which are in each case optionally            substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl,        -   or represents phenoxy-C₁-C₅-alkyl which is optionally            substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl,            or        -   represents pyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C₅-alkyl            or thiazolyloxy-C₁-C₅-alkyl which are in each case            optionally substituted by fluorine, chlorine, bromine, amino            or C₁-C₄-alkyl.        -   R² particularly preferably represents C₁-C₁₆-alkyl,            C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or            poly-C₁-C₆-alkoxy-C₂-C₆-alkyl which are in each case            optionally substituted by fluorine or chlorine,        -   or represents C₃-C₇-cycloalkyl which is optionally            substituted by fluorine, chlorine, C₁-C₄-alkyl or            C₁-C₄-alkoxy, or        -   represents phenyl or benzyl which are in each case            optionally substituted by fluorine, chlorine, bromine,            cyano, nitro, C₁-C₄-alkyl, C₁-C₃-alkoxy, C₁-C₃-halogenoalkyl            or C₁-C₃-halogenoalkoxy.    -   R³ particularly preferably represents C₁-C₆-alkyl which is        optionally substituted by fluorine or chlorine, or phenyl or        benzyl which are in each case optionally substituted by        fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,        C₁-C₂-halogenoalkoxy, C₁-C₂-halogenoalkyl, cyano or nitro.    -   R⁴ and R⁵ independently of one another particularly preferably        represent C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₆-alkylamino,        di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio or C₃-C₄-alkenylthio        which are in each case optionally substituted by fluorine or        chlorine, or represent phenyl, phenoxy or phenylthio which are        in each case optionally substituted by fluorine, chlorine,        bromine, nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-halogenoalkoxy,        C₁-C₃-alkylthio, C₁-C₃-halogenoalkylthio, C₁-C₃-alkyl or        C₁-C₃-halogenoalkyl.    -   R⁶ and R⁷ independently of one another particularly preferably        represent hydrogen, or represent C₁-C₆-alkyl, C₃-C₆-cycloalkyl,        C₁-C₆-alkoxy, C₃-C₆-alkenyl or C₁-C₆-alkoxy-C₂-C₆-alkyl which        are in each case optionally substituted by fluorine or chlorine,        or represent phenyl or benzyl which are in each case optionally        substituted by fluorine, chlorine, bromine, C₁-C₅-halogenoalkyl,        C₁-C₅-alkyl or C₁-C₅-alkoxy, or together represent a        C₃-C₆-alkylene radical which is optionally substituted by        C₁-C₄-alkyl and in which one methylene group is optionally        replaced by oxygen or sulphur.    -   R¹³ particularly preferably represents hydrogen, or C₁-C₆-alkyl        or C₁-C₆-alkoxy which are in each case optionally substituted by        fluorine or chlorine, or represents C₃-C₇-cycloalkyl which is        optionally substituted by fluorine, C₁-C₂-alkyl or C₁-C₂-alkoxy        and in which one methylene group is optionally replaced by        oxygen or sulphur, or represents phenyl, phenyl-C₁-C₃-alkyl or        phenyl-C₁-C₂-alkyloxy which are in each case optionally        substituted by fluorine, chlorine, bromine, C₁-C₅-alkyl,        C₁-C₅-alkoxy, C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy, nitro        or cyano.    -   R¹⁴ particularly preferably represents hydrogen or C₁-C₆-alkyl,        or    -   R¹³ and R¹⁴ together particularly preferably represent        C₄-C₆-alkanediyl.    -   R¹⁵ and R¹⁶ are identical or different and particularly        preferably represent C₁-C₄-alkyl, or    -   R¹⁵ and R¹⁶ together particularly preferably represent a        C₂-C₃-alkanediyl radical which is optionally substituted by        C₁-C₄-alkyl or by phenyl which is optionally substituted by        fluorine, chlorine, bromine, C₁-C₂-alkyl, C₁-C₂-halogenoalkyl,        C₁-C₂-alkoxy, C₁-C₂-halogenoalkoxy, nitro or cyano.    -   X especially preferably represents fluorine, chlorine, bromine,        methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl,        methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,        trifluoromethoxy, difluoromethoxy, cyano or nitro,    -   Y especially preferably represents hydrogen, fluorine, chlorine,        bromine, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl,        tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy,        trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or        nitro,    -   Z especially preferably represents fluorine, chlorine, bromine,        methyl, ethyl, propyl, butyl, iso-butyl, iso-propyl, tert-butyl,        methoxy, ethoxy, propoxy, iso-propoxy, trifluoromethyl,        trifluoromethoxy, difluoromethoxy, cyano or nitro, or    -   Y and Z, together especially preferably represent        C₃-C₄-alkanediyl which is optionally substituted by fluorine,        chlorine, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy,        propoxy, iso-propoxy or trifluoromethyl and in which two members        which are not directly adjacent are optionally replaced by        oxygen, X having one of the abovementioned meanings.    -   Het especially preferably represents one of the groups    -   A especially preferably represents hydrogen, or represents        C₁-C₈-alkyl, C₂-C₄-alkenyl, C₁-C₆-alkoxy-C₁-C₄-alkyl,        poly-C₁-C₄-alkoxy-C₁-C₄-alkyl or C₁-C₆-alkylthio-C₁-C₄-alkyl        which are in each case optionally substituted by fluorine or        chlorine, or represents C₃-C₆-cycloalkyl which is optionally        substituted by fluorine, chlorine, methyl or methoxy and in        which one or two methylene groups are optionally replaced by        oxygen and/or sulphur, or represents phenyl, pyridyl or benzyl        which are in each case optionally substituted by fluorine,        chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, methoxy,        ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.    -   B especially preferably represents hydrogen, C₁-C₈-alkyl or        C₁-C₄-alkoxy-C₁-C₂-alkyl or    -   A, B and the carbon atom to which they are bonded especially        preferably represent C₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl,        wherein in each case one methylene group is optionally replaced        by oxygen or sulphur and which are optionally substituted by        methyl, ethyl, n-propyl, iso-propyl, butyl, isobutyl, sec-butyl,        tert-butyl, cyclohexyl, trifluoromethyl, methoxy, ethoxy,        n-propoxy, iso-propoxy, butoxy, iso-butoxy, sec-butoxy,        tert-butoxy, methylthio, ethylthio, fluorine, chlorine or        phenyl, or    -   A, B and the carbon atom to which they are bonded especially        preferably represent C₅-C₆-cycloalkyl which is substituted by an        alkylenediyl group which optionally contains an oxygen or        sulphur atom or by an alkylenedioxyl group, this substituent        forming a further five- or six-membered ring with the carbon        atom to which it is bonded, or    -   A, B and the carbon atom to which they are bonded especially        preferably represent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in        which two substituents, together with the carbon atoms to which        they are bonded, represent C₃-C₄-alkanediyl, C₃-C₄-alkenediyl or        butadienediyl, wherein in each case one methylene group is        optionally replaced by oxygen or sulphur.    -   D especially preferably represents hydrogen, or represents        C₁-C₈-alkyl, C₃-C₄-alkenyl, C₃-C₄-alkinyl,        C₁-C₆-alkoxy-C₂-C₄-alkyl, poly-C₁-C₄-alkoxy-C₂-C₄-alkyl,        C₁-C₄-alkylthio-C₂-C₄-alkyl or C₃-C₆-cycloalkyl which are in        each case optionally substituted by fluorine or chlorine and in        which one or two methylene groups which are not directly        adjacent are optionally replaced by oxygen and/or sulphur, or        represent phenyl, furanyl, pyridyl, thienyl or benzyl which are        in each case optionally substituted by fluorine, chlorine,        bromine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy,        trifluoromethyl, trifluoromethoxy, cyano or nitro, or    -   A and D together especially preferably represent a        C₃-C₅-alkanediyl or C₃-C₅-alkenediyl group wherein in each case        one methylene group is optionally replaced by oxygen or sulphur        and which are optionally substituted by fluorine, chlorine or by        C₁-C₆-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₃-C₆-cycloalkyl,        phenyl or benzyloxy which are in each case optionally        substituted by fluorine or chlorine.    -   G especially preferably represents hydrogen (a), or represents        one of the groups        -   in which        -   E represents one metal ion equivalent or an ammonium ion,        -   L represents oxygen or sulphur and        -   M represents oxygen or sulphur.    -   R¹ especially preferably represents C₁-C₁₄-alkyl,        C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₆-alkyl,        C₁-C₄-alkylthio-C₁-C₆-alkyl or poly-C₁-C₄-alkoxy-C₁-C₄-alkyl        which are in each case optionally substituted by fluorine or        chlorine, or represents C₃-C₆-cycloalkyl which is optionally        substituted by fluorine, chlorine, methyl, ethyl, n-propyl,        i-propyl, n-butyl, i-butyl, tert-butyl, methoxy, ethoxy,        n-propoxy or iso-propoxy and in which one or two methylene        groups are optionally replaced by oxygen and/or sulphur,        -   or represents phenyl which is optionally substituted by            fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,            n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl,            trifluoromethoxy, methylthio, ethylthio, methylsulphonyl or            ethylsulphonyl,        -   or represents benzyl which is optionally substituted by            fluorine, chlorine, bromine, methyl, ethyl, n-propyl,            i-propyl, methoxy, ethoxy, trifluoromethyl or            trifluoromethoxy,        -   or represents furanyl, thienyl or pyridyl which are in each            case optionally substituted by fluorine, chlorine, bromine,            methyl or ethyl,        -   or represents phenoxy-C₁-C₄-alkyl which is optionally            substituted by fluorine, chlorine, methyl or ethyl, or        -   represents pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl            or thiazolyloxy-C₁-C₄-alkyl which are in each case            optionally substituted by fluorine, chlorine, amino, methyl            or ethyl.    -   R² especially preferably represents C₁-C₁₄-alkyl,        C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl or        poly-C₁-C₄-alkoxy-C₂-C₆-alkyl which are in each case optionally        substituted by fluorine or chlorine,        -   or represents C₃-C₆-cycloalkyl which is optionally            substituted by fluorine, chlorine, methyl, ethyl, n-propyl,            iso-propyl or methoxy,        -   or represents phenyl or benzyl which are in each case            optionally substituted by fluorine, chlorine, cyano, nitro,            methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy,            trifluoromethyl or trifluoromethoxy.    -   R³ especially preferably represents methyl, ethyl, propyl,        iso-prpyl, butyl or tert-butyl which are optionally substituted        by fluorine or chlorine, or phenyl or benzyl which are in each        case optionally substituted by fluorine, chlorine, bromine,        methyl, ethyl, iso-propyl, tert-butyl, methoxy, ethoxy,        iso-propoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro.    -   R⁴ and R⁵ independently of one another especially preferably        represent C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,        di-(C₁-C₄-alkyl)amino or C₁-C₄-alkylthio which are in each case        optionally substituted by fluorine or chlorine, or represent        phenyl, phenoxy or phenylthio which are in each case optionally        substituted by fluorine, chlorine, bromine, nitro, cyano,        methyl, methoxy, trifluoromethyl or trifluoromethoxy.    -   R⁶ and R⁷ independently of one another especially preferably        represent hydrogen, or represent C₁-C₄-alkyl, C₃-C₆-cycloalkyl,        C₁-C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄-alkoxy-C₂-C₄-alkyl which        are in each case optionally substituted by fluorine or chlorine,        or represent phenyl or benzyl which are in each case optionally        substituted by fluorine, chlorine, bromine, methyl, methoxy or        trifluoromethyl, or together represent a C₅-C₆-alkylene radical        which is optionally substituted by methyl or ethyl and in which        one methylene group is optionally replaced by oxygen or sulphur.

The abovementioned general definitions of radicals and explanations orthose given in preferred ranges can be combined with one another asdesired, that is to say also between the particular ranges and preferredranges. They apply accordingly to the end products and to the precursorsand intermediate products.

The compounds of the formula (I) in which a combination of the meaningsgiven above as preferred (preferably) is present are preferred accordingto the invention.

The compounds of the formula (I) in which a combination of the meaningsgiven above as particularly preferred is present are particularlypreferred according to the invention.

The compounds of the formula (I) in which a combination of the meaningsgiven above as especially preferred is present are especially preferredaccording to the invention.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl,also in combination with heteroatoms, such as, for example, in alkoxy,can in each case be straight-chain or branched where possible.

Optionally substituted radicals can be mono- or polysubstituted, and thesubstituents can be identical or different in the case ofpolysubstitutions.

The following compounds of the formula (I-1-a) may be mentionedspecifically, in addition to the compounds mentioned in the preparationexamples:

TABLE 1

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂O—(CH₂)₂——(CH₂)₂S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi-C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO-C₃H₇—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

X = CH₃; Y = CH₃; Z = CH₃

-   -   Table 2: A and B have the same meaning as in Table 1, with        X═CH₃; Y═Cl; Z═CH₃    -   Table 3: A and B have the same meaning as in Table 1, with X═Cl;        Y═Cl; Z═Cl

The following compounds of the formula (I-2-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples:

TABLE 4

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHOC₃H₇—(CH₂)₂——(CH₂)₂—CHiO—C₃H₇—(CH₂)₂— —CH₂—(CHCH₃)₂—(CH₂)₂—

X = CH₃; Y = CH₃; Z = CH₃

-   -   Table 5: A and B have the same meaning as in Table 4, with        X═CH₃; Y═Cl; Z═CH₃    -   Table 6: A and B have the same meaning as in Table 4, with X═Cl;        Y═Cl; Z═Cl

The following compounds of the formula (I-3-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples:

TABLE 7

A B CH₃ H C₂H₅ H C₃H₇ H i-C₃H₇ H C₄H₉ H i-C₄H₉ H s-C₄H₉ H t-C₄H₉ H CH₃CH₃ C₂H₅ CH₃ C₃H₇ CH₃ i-C₃H₇ CH₃ C₄H₉ CH₃ i-C₄H₉ CH₃ s-C₄H₉ CH₃ t-C₄H₉CH₃ C₂H₅ C₂H₅ C₃H₇ C₃H₇

CH₃

CH₃

CH₃ —(CH₂)₂— —(CH₂)₄— —(CH₂)₅— —(CH₂)₆— —(CH₂)₇— —(CH₂)₂—O—(CH₂)₂——(CH₂)₂—S—(CH₂)₂— —CH₂—CHCH₃—(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂——(CH₂)₂—CHC₂H₅—(CH₂)₂— —(CH₂)₂—CHC₃H₇—(CH₂)₂— —(CH₂)₂—CHi—C₃H₇—(CH₂)₂——(CH₂)₂—CHOCH₃—(CH₂)₂— —(CH₂)₂—CHOC₂H₅—(CH₂)₂— —(CH₂)₂—CHiO—C₃H₇—(CH₂)₂——CH₂—(CHCH₃)₂—(CH₂)₂—

X = CH₃ ; Y = CH₃; Z = CH₃

-   -   Table 8: A and B have the same meaning as in Table 7, with        X═CH₃; Y═Cl; Z═CH₃    -   Table 9: A and B have the same meaning as in Table 7, with X═Cl;        Y═Cl; Z═Cl

The following compounds of the formula (I-4-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples:

TABLE 10

A D H CH₃ H C(CH₃)₃ H C(CH₃)₂CH₂Cl CH₃ CH₃ CH₃ CH₂CHCH₃CH₂CH₃ HCH═C(CH₃)₂ CH₃

CH₃

CH₃

CH₃

CH₃

CH₃ H

CH₃

CH₃

CH₃

CH₃

H

CH₃ C₅H₉ CH₃ C₃H₅ H C₃H₄Cl (CH₂)₃ (CH₂)₄ C(CH₃)₂OC(CH₃)₂ X = CH₃ ; Y =CH₃; Z = CH₃

-   -   Table 11: A and D have the same meaning as in Table 10, with        X═CH₃; Y═Cl; Z═CH₃    -   Table 12: A and D have the same meaning as in Table 10, with        X═Cl; Y═Cl; Z═Cl

The following compounds of the formula (I-5-a) may be mentionedspecifically in addition to the compounds mentioned in the preparationexamples:

TABLE 3

A CH₃ CH(CH₃)₂

X = CH₃ ; Y = CH₃; Z = CH₃

-   -   Table 14: A has the same meaning as in Table 13, with X═CH₃,        Y═Cl; Z═CH₃    -   Table 15: A has the same meaning as in Table 13, with X═Cl;        Y═Cl; Z═Cl

If ethylN-[(4,5-dichloro-2-methyl)-phenylacetyl]-1-amino-4-ethyl-cyclohexanecarboxylateis used as the starting substance according to process (A), the courseof the process according to the invention can be represented by thefollowing equation:

If ethyl O-[(2,5-dichloro-4-methyl)-phenylacetyl]-hydroxyacetate is usedaccording to process (B), the course of the process according to theinvention can be represented by the following equation:

If ethyl2-[(2-chloro-4,5-dimethyl)-phenyl]-4-(4-methoxy)-benzylmercapto-4-methyl-3-oxo-valerateis used according to process (C), the course of the process according tothe invention can be represented by the following equation:

If, for example,(chlorocarbonyl)-2-[(4,5-dichloro-2-methyl)-phenyl]-ketene and acetoneare used as starting compounds according to process (D), the course ofthe process according to the invention can be represented by thefollowing equation:

If, for example, (chlorocarbonyl)-2-[(2,4,5-trimethyl)-phenyl]-keteneand thiobenzamide are used as starting compounds according to process(E), the course of the process according to the invention can berepresented by the following equation:

If 3-[(2,5-dichloro-4-methyl)-phenyl]-5,5-dimethyl-pyrrolidine-2,4-dione and pivaloyl chloride are used as starting substances according toprocess (Fα), the course of the process according to the invention canbe represented by the following equation:

If 3-[(2,4,5-trichloro)-phenyl]-4-hydroxy-5-phenyl-Δ³-dihydrofuran-2-oneand acetic anhydride are used as starting compounds according to process(F) (variant β), the course of the process according to the inventioncan be represented by the following equation:

If8-[(2,4-dichloro-5-methyl)-phenyl]-5,5-pentamethylene-pyrrolidine-2,4-dioneand ethoxyethyl chloroformate are used as starting compounds accordingto process (G), the course of the process according to the invention canbe represented by the following equation:

If 3-[(2-bromo-4,5-dimethyl)-phenyl]-4-hydroxy-6-(3-pyridyl)-pyrone andmethyl chloromonothioformate are used as starting substances accordingto process (H) (variant α), the course of the reaction can berepresented as follows:

If5-[(5-chloro-2-fluoro-4-methyl)-phenyl]-6-hydroxy-2-(4-chlorophenyl)-thiazin-4-one,carbon disulphide and methyl iodide are used as starting componentsaccording to process (H) (variant β), the course of the reaction can berepresented as follows:

If2-[(2,4,5-trimethyl)-phenyl]-5,5-[(3-methyl)-pentamethylene]-pyrrolidine-2,4-dioneand methanesulphonyl chloride are used as starting substances accordingto process (I), the course of the reaction can be represented by thefollowing equation:

If2-[(2-chloro-4,5-dimethyl)-phenyl]-4-hydroxy-5-methyl-6-(2-pyridyl)-pyroneand methanethio-phosphonic acid chloride 2,2,2-trifluoroethyl ester areused as starting substances according to process (J), the course of thereaction can be represented by the following equation:

If3-[(2,4,5-trichloro)-phenyl]-5-cyclopropyl-5-methyl-pyrrolidine-2,4-dioneand NaOH are used as components according to process (K), the course ofthe process according to the invention can be represented by thefollowing equation:

If3-[(2-chloro-4-bromo-5-methyl)-phenyl]-4-hydroxy-5,5-tetramethylene-Δ³-dihydro-furan-2-oneand ethyl isocyanate are used as starting substances according toprocess (L) (variant α), the course of the reaction can be representedby the following equation:

If 3-[(2-chloro-4,5-dimethyl)-phenyl]-5-methyl-pyrrolidine-2,4-dione anddimethylcarbamoyl chloride are used as starting substances according toprocess (L) (variant β), the course of the reaction can be representedby the following equation:

The compounds of the formula (II)

in which

-   -   A, B, X, Y, Z and R⁸ have the abovementioned meanings,    -   required as starting substances in process (A) according to the        invention are new.

The acylamino acid esters of the formula (II) are obtained, for example,when amino acid derivatives of the formula (XIX)

in which

-   -   A, B and R⁸ have the abovementioned meanings,    -   are acylated with substituted phenylacetic acid halides of the        formula (XX)        in which    -   X, Y and Z have the abovementioned meanings and    -   Hal represents chlorine or bromine    -   (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem.        6, 341-5, 1968)    -   or when acylamino acids of the formula (XXI)        in which    -   A, B, X, Y and Z have the abovementioned meanings,    -   are esterified (Chem. Ind. (London) 1568 (1968)).

The compounds of the formula (XXI)

in which

-   -   A, B, X, Y and Z have the abovementioned meanings, are new.

The compounds of the formula (XXI) are obtained when amino acids of theformula (XXII)

in which

-   -   A and B have the abovementioned meanings,    -   are acylated with substituted phenylacetic acid halides of the        formula (XX)        in which    -   X, Y and Z have the abovementioned meanings and    -   Hal represents chlorine or bromine,    -   in a Schotten-Baumann reaction (Organikum, VEB Deutscher Verlag        der Wissenschaften, Berlin 1977, page 505).

The compounds of the formula (XX) are new in some cases and they can beprepared by known processes.

The compounds of the formula (XX) are obtained, for example, by aprocedure in which substituted phenylacetic acids of the formula (XXIII)

in which

-   -   X, Y and Z have the abovementioned meaning,    -   are reacted with halogenating agents (for example thionyl        chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus        trichloride, phosphorus tribromide or phosphorus pentachloride),        if appropriate in the presence of a diluent (for example        optionally chlorinated aliphatic or aromatic hydrocarbons, such        as toluene or methylene chloride), at temperatures from −20° C.        to 150° C., preferably from −10° C. to 100° C.

The compounds of the formula (XXIII) are new in some cases, and they canbe prepared by processes known from the literature (Organikum 15thedition, page 533, VEB Deutscher Verlag der Wissenschaften, Berlin1977). The compounds of the formula (XXIII) are obtained, for example,by a procedure in which substituted phenylacetic acid esters of theformula (XXIV)

in which

-   -   X, Y, Z and R⁸ have the abovementioned meaning,    -   are hydrolysed in the presence of an acid (for example an        inorganic acid, such as hydrochloric acid) or a base (for        example an alkali metal hydroxide, such as sodium hydroxide or        potassium hydroxide) and if appropriate a diluent (for example        an aqueous alcohol, such as methanol or ethanol) at temperatures        between 0° C. and 150° C., preferably between 20° C. and 100° C.

The compounds of the formula (XXIV) are new in some cases and they canbe prepared by processes which are known in principle.

The compounds of the formula (XXIV) are obtained, for example, by aprocedure in which substituted 1,1,1-trichloro-2-phenylethanes of theformula (XXV)

in which

-   -   X, Y and Z have the abovementioned meaning,    -   are reacted first with alcoholates (for example alkali metal        alcoholates, such as sodium methylate or sodium ethylate) in the        presence of a diluent (for example the alcohol derived from the        alcoholate) at temperatures between 0° C. and 150° C.,        preferably between 20° C. and 120° C., and then with an acid        (preferably an inorganic acid, such as, for example, sulphuric        acid) at temperatures between −20° C. and 150° C., preferably        0° C. and 100° C. (cf DE 3 314 249).

The compounds of the formula (XXV) are new in some cases and they can beprepared by processes which are known in principle.

The compounds of the formula (XXV) are obtained, for example, whenanilines of the formula (XXVI)

in which

-   -   X, Y and Z have the abovementioned meaning,    -   are reacted with vinylidene chloride (CH₂═CCl₂) in the presence        of an alkyl nitrite of the formula (XXVII)        R²¹—ONO  (XXVII)        in which    -   R²¹ represents alkyl, preferably C₁-C₆-alkyl,    -   in the presence of copper(II) chloride and if appropriate in the        presence of a diluent (for example an aliphatic nitrite, such as        acetonitrile), at a temperature of −20° C. to 80° C., preferably        0° C. to 60° C.

The compounds of the formula (XXVI) and (XXVII) are known compounds oforganic chemistry. Copper(II) chloride and vinylidene chloride have beenknown and commercially obtainable for a long time.

The compounds of the formula (XIX) and (XXII) are known in some casesand/or they can be prepared by known processes (see, for example,Compagnon, Miocque Ann. Chim. (Paris) [14] 5, pages 11-22, 23-27(1970)).

The substituted cyclic aminocarboxylic acids of the formula (XXIIa) inwhich A and B form a ring are in general obtainable by theBucherer-Bergs synthesis or by the Strecker synthesis and are in eachcase obtained in these syntheses in different isomer forms. Thus, underthe conditions of the Bucherer-Bergs synthesis, the isomers (forsimplicity called β below) in which the radicals R and the carboxylgroup are equatorial are predominantly obtained, while under theconditions of the Strecker synthesis the isomers (for simplicity calleda below) in which the amino group and the radicals R are equatorial arepredominantly obtained.

(L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can.J. Chem. 53, 3339 (1975)).

Furthermore, the starting substances of the formula (II)

in which

-   -   A, B, X, Y, Z and R⁸ have the abovementioned meanings,    -   used in the above process (A) can be prepared when aminonitriles        of the formula (XXVIII)        in which    -   A and B have the abovementioned meanings,    -   are reacted with substituted phenylacetic acid halides of the        formula (XX)        in which    -   X, Y, Z and H have the abovementioned meanings,    -   to give compounds of the formula (XXIX)        in which    -   A, B, X, Y and Z have the abovementioned meanings,    -   and these are then subjected to acid alcoholysis.

The compounds of the formula (XXIX) are likewise new.

The compounds of the formula (III)

in which

-   -   A, B, X, Y, Z and R⁸ have the abovementioned meanings,    -   required as starting substances in process (B) according to the        invention are new.

They can be prepared in a simple manner by methods which are known inprinciple.

The compounds of the formula (III) are obtained, for example, when

2-hydroxycarboxylic acid esters of the formula (XXX)

in which

-   -   A, B and R⁸ have the abovementioned meanings,    -   are acylated with substituted phenylacetic acid halides of the        formula (XX)        in which    -   X, Y, Z and Hal have the abovementioned meanings    -   (Chem. Reviews 52, 237-416 (1953)).

Compounds of the formula (III) are furthermore obtained when substitutedphenylacetic acids of the formula (XXII)

in which

-   -   X, Y and Z have the abovementioned meanings,    -   are alkylated with α-halogenocarboxylic acid esters of the        formula (XXXI)        in which    -   A, B and R⁸ have the abovementioned meanings and    -   Hal represents chlorine or bromine.

The compounds of the formula (XXXI) are commercially obtainable.

The compounds of the formula (IV)

in which

-   -   A, B, W, X, Y, Z and R⁸ have the abovementioned meanings,    -   required as starting substances in the above process (C) are        new.

They can be prepared by methods which are known in principle.

The compounds of the formula (IV) are obtained, for example, whensubstituted phenylacetic acid esters of the formula (XXIV)

in which

-   -   X, Y, R⁸ and Z have the abovementioned meanings,    -   are acylated with 2-benzylthio-carboxylic acid halides of the        formula (XXXII)        in which    -   A, B and W have the abovementioned meanings and    -   Hal represents halogen (in particular chlorine or bromine),    -   in the presence of strong bases (see, for example, M. S.        Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem.        Commun., (1987), 1228).

The benzylthio-carboxylic acid halides of the formula (XXXII) are knownin some cases and/or they can be prepared by known processes (J.Antibiotics (1983), 26, 1589).

The halogenocarbonylketenes of the formula (VI) required as startingsubstances in process (D) are new. They can be prepared in a simplemanner by methods which are known in principle (cf., for example, Org.Prep. Proced. Int., 7, (4), 155-158, 1975 and DE 1 945 703). Thecompounds of the formula (VI)

in which

-   -   X, Y and Z have the abovementioned meanings and    -   Hal represents chlorine or bromine,    -   are obtained when    -   substituted phenylmalonic acids of the formula (XXXIII)        in which    -   X, Y and Z have the abovementioned meanings,    -   are reacted with acid halides, such as, for example, thionyl        chloride, phosphorus(V) chloride, phosphorus(III) chloride,        oxalyl chloride, phosgene or thionyl bromide, if appropriate in        the presence of catalysts, such as, for example,        diethylformamide, methyl-stearylformamide or triphenylphosphine,        and if appropriate in the presence of bases, such as, for        example, pyridine or triethylamine, at a temperature between        −20° C. and 200° C., preferably between 0° C. and 150° C.

The substituted phenylmalonic acids of the formula (XXXIII) are new.However, they can be prepared in a simple manner by known processes(cf., for example, Organikum, VEB Deutscher Verlag der Wissenschaften,Berlin 1977, page 517 et seq.), for example from substitutedphenylmalonic acid esters of the formula (XXXIV)

in which

-   -   X, Y, Z and R⁸ have the abovementioned meaning,    -   by hydrolysis.

The carbonyl compounds of the formula (V) or silylenol ethers thereof ofthe formula (Va)

in which

-   -   A, D and R^(8′) have the abovementioned meanings,    -   required as starting substances for process (E) according to the        invention are commercially obtainable compounds which are        generally known or accessible by known processes.

The preparation of the ketene acid chlorides of the formula (VI)required as starting substances for carrying out process (E) accordingto the invention has already been described in the case of process (D)according to the invention. The thioamides of the formula (VII)

in which

-   -   A has the abovementioned meaning,    -   required for carrying out process (E) according to the invention        are compounds which are generally known in organic chemistry.

The malonic acid esters of the formula (XXXIV)

in which

-   -   R⁸, X, Y and Z have the abovementioned meanings,    -   are new and can be prepared by generally known methods of        organic chemistry (cf., for example, Tetrahedron Lett. 27,        2763(1986) and Organikum VEB Deutscher Verlag der        Wissenschaften, Berlin 1977, page 587 et seq.).

The acid halides of the formula (VIII), carboxylic acid anhydrides ofthe formula (IX), chloroformic acid esters or chloroformic acidthioesters of the formula (X), chloromonothioformic acid esters orchlorodithioformic acid esters of the formula (XI), alkyl halides of theformula (XII), sulphonic acid chlorides of the formula (XIII),phosphorus compounds of the formula (XIV) and metal hydroxides, metalalkoxides or amines of the formula (XV) and (XVI) and isocyanates of theformula (XVII) and carbamic acid chlorides of the formula (XVIII)furthermore required as starting substances for carrying out processes(F), (G), (H), (I), (J), (K) and (L) according to the invention aregenerally known compounds of organic or inorganic chemistry.

The compounds of the formulae (V), (VII) to (XVIII), (XIX), (XXII),(XXVIII), (XXX), (XXXI), (XXXII), (XXXIII) and (XXXIV) are furthermoreknown from the patent applications cited above and/or can be prepared bythe methods mentioned therein.

Process (A) is characterized in that compounds of the formula (II) inwhich A, B, X, Y, Z and R⁸ have the abovementioned meanings aresubjected to intramolecular condensation in the presence of a diluentand in the presence of a base.

Diluents which can be employed in process (A) according to the inventionare all the organic solvents which are inert towards the reactionparticipants. Solvents which can preferably be used are hydrocarbons,such as toluene and xylene, and furthermore ethers, such as dibutylether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycoldimethyl ether, and also polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide and N-methyl-pyrrolidone, as well asalcohols, such as methanol, ethanol, propanol, iso-propanol, butanol,iso-butanol and tert-butanol.

All the customary proton acceptors can be employed as the base(deprotonating agent) in carrying out process (A) according to theinvention. Proton acceptors which can preferably be used are alkalimetal and alkaline earth metal oxides, hydroxides and carbonates, suchas sodium hydroxide, potassium hydroxide, magnesium oxide, calciumoxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be employed in the presence of phase transfer catalysts,such as, for example, triethylbenzylammonium chloride,tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C₈-C₁₀)ammoniumchloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). Alkali metals,such as sodium or potassium, can moreover be used. Alkali metal andalkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and in addition also alkali metalalcoholates, such as sodium methylate, sodium ethylate and potassiumtert-butylate, can furthermore be employed.

The reaction temperature can be varied within a substantial range whencarrying out process (A) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (A) according to the invention is in general carried out undernormal pressure.

In carrying out process (A) according to the invention, the reactioncomponent of the formula (II) and the deprotonating base are in generalemployed in equimolar to about twice the equimolar amounts. However, itis also possible to use one or other of the components in a largerexcess (up to 3 mol).

Process (B) is characterized in that compounds of the formula (III) inwhich A, B, X, Y, Z and R⁸ have the abovementioned meanings aresubjected to intramolecular condensation in the presence of a diluentand in the presence of a base.

Diluents which can be employed in process (B) according to the inventionare all the organic solvents which are inert towards the reactionparticipants. Solvents which can preferably be used are hydrocarbons,such as toluene and xylene, and furthermore ethers, such as dibutylether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycoldimethyl ether, and also polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide and N-methyl-pyrrolidone. Alcohols, suchas methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol andtert-butanol, can furthermore be employed.

All the customary proton acceptors can be employed as the base(deprotonating agent) in carrying out process (B) according to theinvention. Proton acceptors which can preferably be used are alkalimetal and alkaline earth metal oxides, hydroxides and carbonates, suchas sodium hydroxide, potassium hydroxide, magnesium oxide, calciumoxide, sodium carbonate, potassium carbonate and calcium carbonate,which can also be employed in the presence of phase transfer catalysts,such as, for example, triethylbenzylammonium chloride,tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C₈-C₁₀)ammoniumchloride) or TDA 1 (=tris-(methoxyethoxyethyl)-amine). Alkali metals,such as sodium or potassium, can moreover be used. Alkali metal andalkaline earth metal amides and hydrides, such as sodium amide, sodiumhydride and calcium hydride, and in addition also alkali metalalcoholates, such as sodium methylate, sodium ethylate and potassiumtert-butylate, can furthermore be employed.

The reaction temperature can be varied within a substantial range whencarrying out process (B) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (B) according to the invention is in general carried out undernormal pressure.

In carrying out process (B) according to the invention, the reactioncomponents of the formula (III) and the deprotonating bases are ingeneral employed in approximately equimolar amounts. However, it is alsopossible to use one or other of the components in a larger excess (up to3 mol).

Process (C) is characterized in that compounds of the formula (IV) inwhich A, B, W, X, Y, Z and R⁸ have the abovementioned meaning aresubjected to intramolecular cyclization in the presence of an acid andif appropriate in the presence of a diluent.

Diluents which can be employed in process (C) according to the inventionare all the organic solvents which are inert towards the reactionparticipants. Solvents which can preferably be used are hydrocarbons,such as toluene and xylene, and furthermore halogenated hydrocarbons,such as methylene chloride, chloroform, ethylene chloride, chlorobenzeneand dichlorobenzene, and also polar solvents, such as dimethylsulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone.Alcohols, such as methanol, ethanol, propanol, iso-propanol, butanol,iso-butanol and tert-butanol, can furthermore be employed.

If appropriate, the acid employed can also serve as the diluent.

Acids which can be employed in process (C) according to the inventionare all the customary inorganic and organic acids, such as, for example,hydrogen halide acids, sulphuric acid and alkyl-, aryl- andhaloalkylsulphonic acids, and halogenated alkylcarboxylic acids, suchas, for example, trifluoroacetic acid, are used in particular.

The reaction temperature can be varied within a substantial range incarrying out process (C) according to the invention. The reaction is ingeneral carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 150° C.

Process (C) according to the invention is in general carried out undernormal pressure.

In carrying out process (C) according to the invention, the reactioncomponents of the formula (IV) and the acid are employed, for example,in equimolar amounts. Where appropriate, however, it is also possible toemploy the acid in catalytic amounts.

Process (D) according to the invention is characterized in that carbonylcompounds of the formula (V) or silylenol ethers thereof of the formula(Va) are reacted with ketene acid halides of the formula (VI), ifappropriate in the presence of a diluent and if appropriate in thepresence of an acid acceptor.

Diluents which can be employed in process (D) according to the inventionare all the organic solvents which are inert towards the reactionparticipants. Solvents which can preferably be used are hydrocarbons,such as o-dichlorobenzene, tetralin, toluene and xylene, and furthermoreethers, such as dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, and also polar solvents, such as dimethyl sulphoxide,sulpholane, dimethylformamide or N-methyl-pyrrolidone.

All the customary acid acceptors can be used as acid acceptors incarrying out process (D) according to the invention.

Acid acceptors which can preferably be used are tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base orN,N-dimethyl-aniline.

The reaction temperature can be varied within a substantial range incarrying out process (D) according to the invention. The reaction isexpediently carried out at temperatures between 0° C. and 250° C.,preferably between 50° C. and 220° C.

Process (D) according to the invention is preferably carried out undernormal pressure.

In carrying out process (D) according to the invention, the reactioncomponents of the formulae (V) and (VI) and if appropriate the acidacceptor are in general employed in approximately equimolar amounts.However, it is also possible to use one or other of the components in alarger excess (up to 5 mol).

Process (E) according to the invention is characterized in thatthioamides of the formula (VIII) are reacted with ketene acid halides ofthe formula (VI), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid acceptor.

Diluents which can be employed in process variant (E) according to theinvention are all the inert organic solvents. Solvents which canpreferably be used are hydrocarbons, such as o-dichlorobenzene,tetralin, toluene and xylene, and furthermore ethers, such as dibutylether, glycol dimethyl ether and diglycol dimethyl ether, and also polarsolvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide andN-methyl-pyrrolidone.

All the customary acid acceptors can be used as acid acceptors incarrying out process (E) according to the invention.

Acid acceptors which can preferably be used are tertiary amines, such astriethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base orN,N-dimethyl-aniline.

The reaction temperature can be varied within a substantial range incarrying out process (E) according to the invention. The reaction isexpediently carried out at temperatures between 0° C. and 250° C.,preferably between 20° C. and 220° C.

Process (E) according to the invention is expediently carried out undernormal pressure.

In carrying out process (E) according to the invention, the reactioncomponents of the formulae (VII) and (VI) and if appropriate the acidacceptors are in general employed in approximately equimolar amounts.However, it is also possible to use one or other of the components in alarger excess (up to 5 mol).

Process (Fα) is characterized in that compounds of the formulae (I-1-a)to (I-5-a) are in each case reacted with carboxylic acid halides of theformula (VIII), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid-binding agent.

Diluents which can be employed in process (Fα) according to theinvention are all the solvents which are inert towards the acid halides.Solvents which can preferably be used are hydrocarbons, such as benzine,benzene, toluene, xylene and tetralin, and furthermore halogenatedhydrocarbons, such as methylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones,such as acetone and methyl isopropyl ketone, and furthermore ethers,such as diethyl ether, tetrahydrofuran and dioxane, and moreovercarboxylic acid esters, such as ethyl acetate, and also strongly polarsolvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane.If the stability of the acid halide to hydrolysis allows, the reactioncan also be carried out in the presence of water.

Possible acid-binding agents in the reaction by process (Fα) accordingto the invention are all the customary acid acceptors. Acid acceptorswhich can preferably be used are tertiary amines, such as triethylamine,pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU),diazabicyclononene (DBN), Hünig base and N,N-dimethyl-aniline, andfurthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, and also alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate, as well as alkali metal hydroxides, such as sodium hydroxideand potassium hydroxide.

The reaction temperature can be varied within a substantial range inprocess (Fα) according to the invention. The reaction is in generalcarried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

In carrying out process (Fα) according to the invention, the startingsubstances of the formulae (I-1-a) to (I-5-a) and the carboxylic acidhalide of the formula (VIII) are in general used in amounts which are ineach case approaching equivalent amounts. However, it is also possibleto employ the carboxylic acid halide in a larger excess (up to 5 mol).Working up is carried out by customary methods.

Process (Fβ) is characterized in that compounds of the formulae (I-1-a)to (I-5-a) are in each case reacted with carboxylic acid anhydrides ofthe formula (IX), if appropriate in the presence of a diluent and ifappropriate in the presence of an acid-binding agent.

Diluents which can be used in process (Fβ) according to the inventionare preferably those diluents which are also preferably possible in thecase where acid halides are used. A carboxylic acid anhydride employedin excess can moreover also simultaneously function as the diluent.

Possible acid-binding agents which are added, if appropriate, in process(Fβ) are preferably those acid-binding agents which are also preferablypossible when acid halides are used.

The reaction temperature can be varied within a substantial range inprocess (Fβ) according to the invention. The reaction is in generalcarried out at temperatures between −20° C. and +150° C., preferablybetween 0° C. and 100° C.

In carrying out process (Fβ) according to the invention, the startingsubstances of the formulae (I-1-a) to (I-5-a) and the carboxylic acidanhydride of the formula (IX) are in general used in amounts which arein each case approaching equivalent amounts. However, it is alsopossible to employ the carboxylic acid anhydride in a larger excess (upto 5 mol). Working up is carried out by customary methods.

In general, a procedure is followed in which the diluent and thecarboxylic acid anhydride present in excess as well as the carboxylicacid formed are removed by distillation or by washing with an organicsolvent or with water.

Process (G) is characterized in that compounds of the formulae (I-1-a)to (I-5-a) are in each case reacted with chloroformic acid esters orchloroformic acid thioesters of the formula (X), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

Possible acid-binding agents in process (G) according to the inventionare all the customary acid acceptors. Acid acceptors which canpreferably be used are tertiary amines, such as triethylaamine,pyridine, DABCO, DBU, DBA, Hünig base and N,N-dimethyl-aniline, andfurthermore alkaline earth metal oxides, such as magnesium oxide andcalcium oxide, and also alkali metal and alkaline earth metalcarbonates, such as sodium carbonate, potassium carbonate and calciumcarbonate, as well as alkali metal hydroxides, such as sodium hydroxideand potassium hydroxide.

Diluents which can be employed in process (G) according to the inventionare all the solvents which are inert towards the chloroformic acidesters or chloroformic acid thioesters. Solvents which can preferably beused are hydrocarbons, such as benzine, benzene, toluene, xylene andtetralin, and furthermore halogenated hydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride, chlorobenzene ando-dichlorobenzene, and also ketones, such as acetone and methylisopropyl ketone, and moreover ethers, such as diethyl ether,tetrahydrofuran and dioxane, and furthermore carboxylic acid esters,such as ethyl acetate, and also nitriles, such as acetonitrile, as wellas strongly polar solvents, such as dimethylformamide, dimethylsulphoxide and sulpholane.

The reaction temperature can be varied within a substantial range incarrying out process (G) according to the invention. The reactiontemperature is in general between −20° C. and +100° C., preferablybetween 0° C. and 50° C.

Process (G) according to the invention is in general carried out undernormal pressure.

In carrying out process (G) according to the invention, the startingsubstances of the formulae (I-1-a) to (I-5-a) and the correspondingchloroformic acid esters or chloroformic acid thioesters of the formula(X) are in general used in amounts which are in each case approachingequivalent amounts. However, it is also possible to employ one or otherof the components in a larger excess (up to 2 mol). Working up iscarried out by customary methods. A procedure is in general followed inwhich salts which have precipitated out are removed and the reactionmixture which remains is concentrated by stripping off the diluent.

Process (H) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith (Ha) compounds of the formula (XI) in the presence of a diluent andif appropriate in the presence of an acid-binding agent, or (Hβ) carbondisulphide and then with alkyl halides of the formula (XII), ifappropriate in the presence of a diluent and if appropriate in thepresence of a base.

In preparation process (Hα), about 1 mol of chloromonothioformic acidester or chlorodithioformic acid ester of the formula (XI) is reactedper mol of starting compound of the formulae (I-1-a) to (I-5-a) at 0 to120° C., preferably at 20 to 60° C.

Possible diluents which are added, if appropriate, are all the inertpolar organic solvents, such as ethers, amides, sulphones, sulphoxidesand also halogenoalkanes.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If the enolate salt of the compounds (I-1-a) to (I-5-a) is prepared in apreferred embodiment by addition of strong deprotonating agents, suchas, for example, sodium hydride or potassium tert-butylate, furtheraddition of acid-binding agents can be omitted.

If acid-binding agents are employed, then customary inorganic or organicbases are possible, and examples which may be mentioned are sodiumhydroxide, sodium carbonate, potassium carbonate, pyridine andtriethylamine.

The reaction can be carried out under normal pressure or under increasedpressure, and is preferably carried out under normal pressure. Workingup is carried out by customary methods.

In preparation process (Hβ), in each case the equimolar amount or anexcess of carbon disulphide is added per mol of starting compounds ofthe formulae (I-1-a) to (I-5-a). The reaction here is preferably carriedout at temperatures from 0 to 50° C., and in particular at 20 to 30° C.

It is often expedient first to prepare the corresponding salt from thecompounds of the formulae (I-1-a) to (I-5-a) by addition of a base (suchas, for example, potassium tert-butylate or sodium hydride). Thecompounds (I-1-a) to (I-5-a) are in each case reacted with carbondisulphide until the formation of the intermediate compound has ended,for example after stirring at room temperature for several hours.

All the customary proton acceptors can be employed as bases in process(Hβ). Proton acceptors which can preferably be used are alkali metalhydrides, alkali metal alcoholates, alkali metal or alkaline earth metalcarbonates or bicarbonates or nitrogen bases. Examples which may bementioned are sodium hydride, sodium methanolate, sodium hydroxide,calcium hydroxide, potassium carbonate, sodium bicarbonate,triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline,diazabicyclooctane (DABCO), diazabicyclononene (DBN) anddiazabicycloundecene (DBU).

All the customary solvents can be used as diluents in this process.

Solvents which can preferably be used are aromatic hydrocarbons, such asbenzene or toluene, alcohols, such as methanol, ethanol, isopropanol orethylene glycol, nitriles, such as acetonitrile, ethers, such astetrahydrofuran or dioxane, amides, such as dimethylformamide, or otherpolar solvents, such as dimethyl sulphoxide or sulpholane.

Further reaction with the alkyl halide of the formula (XII) ispreferably carried out at 0 to 70° C., and in particular at 20 to 50° C.At least the equimolar amount of alkyl halide is employed in thisreaction.

The reaction is carried out under normal pressure or under increasedpressure, preferably under normal pressure.

Working up is again carried out by customary methods.

Process (I) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith sulphonic acid chlorides of the formula (XIII), if appropriate inthe presence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (I), about 1 mol of sulphonic acid chloride ofthe formula (XIII) is reacted per mol of starting compound of theformula (I-1-a to I-5-a) at −20 to 150° C., preferably at 0 to 70° C.

Process (I) is preferably carried out in the presence of a diluent.

Possible diluents are all the inert polar organic solvents, such asethers, amides, ketones, carboxylic acid esters, nitriles, sulphones,sulphoxides or halogenated hydrocarbons, such as methylene chloride.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide and methylenechloride are preferably employed.

If the enolate salt of the compounds (I-1-a) to (I-5-a) is prepared in apreferred embodiment by addition of strong deprotonating agents (suchas, for example, sodium hydride or potassium tert-butylate), furtheraddition of acid-binding agents can be omitted.

If acid-binding agents are employed, then customary inorganic or organicbases are possible, and examples which may be mentioned are sodiumhydroxide, sodium carbonate, potassium carbonate, pyridine andtriethylamine.

The reaction can be carried out under normal pressure or under increasedpressure, and is preferably carried out under normal pressure. Workingup is carried out by customary methods.

Process (J) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith phosphorus compounds of the formula (XIV), if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (J), 1 to 2, preferably 1 to 1.3, mol of thephosphorus compound of the formula (XIV) are reacted per mol of thecompounds (I-1-a) to (I-5-a) at temperatures between −40° C. and 150°C., preferably between −10 and 110° C., to give compounds of theformulae (I-1-e) to (I-6-e).

Process (J) is preferably carried out in the presence of a diluent.

Possible diluents are all the inert polar organic solvents, such asethers, carboxylic acid esters, halogenated hydrocarbons, ketones,amides, nitriles, sulphones, sulphoxides and the like.

Acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamideand methylene chloride are preferably employed.

Possible acid-binding agents, which are added if appropriate, are thecustomary inorganic or organic bases, such as hydroxides, carbonates oramines. Examples which may be mentioned are sodium hydroxide, sodiumcarbonate, potassium carbonate, pyridine and triethylamine.

The reaction can be carried out under normal pressure or under increasedpressure, and is preferably carried out under normal pressure. Workingup is carried out by customary methods of organic chemistry. The endproducts are preferably purified by crystallization, chromatographicpurification or by so-called “incipient distillation”, i.e. removal ofthe volatile constituents in vacuo.

Process (K) is characterized in that compounds of the formulae (I-1-a)to (I-5-a) are in each case reacted with metal hydroxides or metalalkoxides of the formula (XV) or amines of the formula (XVI), ifappropriate in the presence of a diluent.

Diluents which can be employed in process (K) according to the inventionare preferably ethers, such as tetrahydrofuran, dioxane or diethylether, or else alcohols, such as methanol, ethanol or isopropanol, oralternatively water. Process (K) according to the invention is ingeneral carried out under normal pressure. The reaction temperature isin general between −20° C. and 100° C., preferably between 0° C. and 50°C.

Process (L) according to the invention is characterized in thatcompounds of the formulae (I-1-a) to (I-5-a) are in each case reactedwith (Lα) compounds of the formula (XVII), if appropriate in thepresence of a diluent and if appropriate in the presence of a catalyst,or with (Lβ) compounds of the formula (XVIII) if appropriate in thepresence of a diluent and if appropriate in the presence of anacid-binding agent.

In preparation process (Lα), about 1 mol of isocyanate of the formula(XVII) is reacted per mol of starting compound of the formulae (I-1-a)to (I-5-a) at 0 to 100° C., preferably at 20 to 50° C.

Process (Lα) is preferably carried out in the presence of a diluent.

Possible diluents are all the inert organic solvents, such as aromatichydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles,sulphones or sulphoxides.

If appropriate, catalysts can be added to accelerate the reaction.Catalysts which can very advantageously be employed are organotincompounds, such as, for example, dibutyltin dilaurate.

The reaction is preferably carried out under normal pressure.

In preparation process (Lβ), about 1 mol of carbamic acid chloride ofthe formula (XVIII) is reacted per mol of starting compound of theformulae (I-1-a) to (I-5-a) at 0 to 150° C., preferably at 20 to 70° C.

Possible diluents, which are added if appropriate, are all the inertpolar organic solvents, such as ethers, carboxylic acid esters,nitriles, ketones, amides, sulphones, sulphoxides or halogenatedhydrocarbons.

Dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylenechloride are preferably employed.

If the enolate salt of the compound (I-1-a) to (I-5-a) is prepared in apreferred embodiment by addition of strong deprotonating agents (suchas, for example, sodium hydride or potassium tert-butylate), furtheraddition of acid-binding agents can be omitted.

If acid-binding agents are employed, customary inorganic or organicbases are possible, and examples which may be mentioned are sodiumhydroxide, sodium carbonate, potassium carbonate, triethylamine orpyridine.

The reaction can be carried out under normal pressure or under increasedpressure, and is preferably carried out under normal pressure. Workingup is carried out by customary methods.

The active compounds are suitable for controlling animal pests,preferably arthropods and nematodes, in particular insects andarachnids, which are encountered in agriculture, in forestry, in theprotection of stored products and of materials, and in the hygienefield. They are active against normally sensitive and resistant speciesand against all or some stages of development. The abovementioned pestsinclude:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Phylloxera vastatrix,Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. andLinognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Acanthoscelides obtectus, Hylotrupes bajulus,Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae,Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis,Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilusspp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallonsolstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compounds according to the invention are distinguished by ahigh insecticidal and acaricidal activity.

They can be employed particularly successfully against insects which areharmful to plants, such as, for example, against the larvae of themustard beetle (Phaedon cochleariae) or against the larvae of the ricegreen leafhopper (Nephotettix cincticeps) and against the larvae of thecabbage moth (Plutella maculipennis).

The active compounds according to the invention can furthermore be usedas defoliants, desiccants, agents for destroying broad-leaved plantsand, especially, as weed-killers. By weeds, in the broadest sense, thereare to be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The dosages of the active compounds according to the invention necessaryfor combating weeds are between 0.001 and 10 kg/ha, preferably between0.005 and 5 kg/ha.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cycnodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hop fields, onornamental and sports lawns and meadow areas and for the selectivecombating of weeds in annual cultures.

The active compounds according to the invention are particularlysuitable for selectively combating monocotyledon weeds in dicotyledoncrops by the pre- and post-emergence method. For example, they can beemployed very successfully for combating harmful grasses in cotton orsugar beet.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As Solid Carriers there are Suitable:

-   -   for example, ammonium salts and ground natural minerals, such as        kaolins, clays, talc, chalk, quartz, attapulgite,        montmorillonite or diatomaceous earth, and ground synthetic        minerals, such as highly disperse silica, alumina and silicates;        as solid carriers for granules there are suitable: for example,        crushed and fractionated natural rocks such as calcite, marble,        pumice, sepiolite and dolomite, as well as synthetic granules of        inorganic and organic meals, and granules of organic material        such as sawdust, coconut shells, maize cobs and tobacco stalks;        as emulsifying and/or foam-forming agents there are suitable:        for example, non-ionic and anionic emulsifiers, such as        polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol        ethers, for example alkylaryl polyglycol ethers, alkyl        sulphonates, alkyl sulphates, aryl sulphonates as well as        albumen hydrolysis products; as dispersing agents there are        suitable: for example, lignin-sulphite waste liquors and        methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms prepared fromthese formulations as a mixture with other active compounds, such asinsecticides, baits, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphoric acid esters, carbamates, carboxylicacid esters, chlorinated hydrocarbons, phenylureas, substances producedby microorganisms, and the like.

Particularly favourable mixing partners are, for example, the following:

Fungicides:

-   -   2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;        2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;        2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide;        (E)-2-methoxyimino-N-methyl-2-(2-phenoxy-phenyl)acetamide;        8-hydroxyquinoline sulphate; methyl        (E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;        methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;        2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine,        azaconazole,    -   benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,        blasticidin-S, bromuconazole, bvpirimate, buthiobate,    -   calcium polysulphide, captafol, captan, carbendazim, carboxin,        quinomethionate, chloroneb, chloropicrin, chlorothalonil,        chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,    -   dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,        diethofencarb, difenoconazole, dimethirimol, dimethomorph,        diniconazole, dinocap, diphenylamine, dipyrithion, ditalimfos,        dithianon, dodine, drazoxolon,    -   edifenphos, epoxyconazole, ethirimol, etridiazole,    -   fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,        fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide,        ferbam, ferimzone, fluazinam, fludioxonil, fluoromide,        fluquinconazole, flusilazole, flusulfamide, flutolanil,        flutriafol, folpet, fosetyl-aluminum, fthalide, fuberidazole,        furalaxyl, furmecyclox,    -   guazatine,    -   hexachlorobenzene, hexaconazole, hymexazol,    -   imazalil, imibenconazole, iminoctadine, iprobenfos (IBP),        iprodione, isoprothiolane,    -   kasugamycin, copper preparations such as: copper hydroxide,        copper naphthenate, copper oxychloride, copper sulphate, copper        oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb,        maneb, mepanipyrim, mepronil, metalaxyl, metconazole,        methasulfocarb, methfuroxam, metiram, metsulfovax, myclobutanil,    -   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,    -   ofurace, oxadixyl, oxamocarb, oxycarboxin,    -   pefurazoate, penconazole, pencycuron, phosdiphen, phthalide,        pimaricin, piperalin, polycarbamate, polyoxin, probenazole,        prochloraz, procymidone, propamocarb, propiconazole, propineb,        pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene        (PCNB),    -   sulphur and sulphur preparations,    -   tebuconazole, tecloftalam, tecnazene, tetraconazole,        thiabendazole, thicyofen, thiophanate-methyl, thiram,        tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,        triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,        triforine, triticonazole,    -   validamycin A, vinclozolin,    -   zineb, ziram        Bactericides:    -   bronopol, dichlorophen, nitrapyrin, nickel        dimethyldithiocarbamate, kasugamycin, octhilinon,        furancarboxylic acid, oxytetracyclin, probenazol, streptomycin,        tecloftalam, copper sulphate and other copper preparations.        Insecticides/Acaricides/Nematicides:    -   abamectin, AC 303 630, acephate, acrinathrin, alanycarb,        aldicarb, alphamethrin, amitraz, avermectin, AZ 60541,        azadirachtin, azinphos A, azinphos M, azocyclotin,    -   Bacillus thuringiensis, bendiocarb, benfuracarb, bensultap,        beta-cyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A,        bufencarb, buprofezin, butocarboxin, butylpyridaben,    -   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,        cartap, CGA 157 419, CGA 184 699, chloethocarb, chlorethoxyfos,        chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos,        chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine,        cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin,        cypermethrin, cyromazine,    -   deltamethrin, demeton-M, demeton-S, demeton-S-methyl,        diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos,        dicrotophos, diethion, diflubenzuron, dimethoate,        dimethylvinphos, dioxathion, disulfoton,    -   edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion,        ethofenprox, ethoprophos, etrimphos,    -   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,        fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad,        fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,        flucycloxuron, flucythrinate, flufenoxuron, flufenprox,        fluvalinate,    -   fonophos, formothion, fosthiazate, fubfenprox, furathiocarb,    -   HCH, heptenophos, hexaflumuron, hexythiazox,    -   imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb,        isoxathion, ivermectin,    -   lambda-cyhalothrin, lufenuron,    -   malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,        methacrifos, methamidophos, methidathion, methiocarb, methomyl,        metolcarb, milbemectin, monocrotophos, moxidectin,    -   naled, NC 184, NI 25, nitenpyram,    -   omethoate, oxamyl, oxydemethon M, oxydeprofos,    -   parathion A, parathion M, permethrin, phenthoate, phorate,        phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos        M, pirimiphos A, profenofos, promecarb, propaphos, propoxur,        prothiofos, prothoate, pymetrozin, pyrachlophos, pyraclofos,        pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum,        pyridaben, pyrimidifen, pyriproxifen,    -   quinalphos,    -   RH 5992,    -   salithion, sebufos, silafluofen, sulfotep, sulprofos,    -   tebufenozid, tebufenpyrad, tebupirimiphos, teflubenzuron,        tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos,        thiafenox, thiodicarb, thiofanox, thiomethon, thionazin,        thuringiensin, tralomethrin, triarathen, triazophos, triazuron,        trichlorfon, triflumuron, trimethacarb,    -   vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.        Herbicides:    -   for example anilides, such as, for example, diflufenican and        propanil; arylcarboxylic acids such as, for example,        dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic        acids, such as, for example, 2,4 D, 2,4 DB, 2,4 DP, fluroxypyr,        MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic acid esters,        such as, for example, diclofop-methyl, fenoxaprop-ethyl,        fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl;        azinones, such as, for example, chloridazon and norflurazon;        carbamates, such as, for example, chlorpropham, desmedipham,        phenmedipham and propham; chloroacetanilides, such as, for        example, alachlor, acetochlor, butachlor, metazachlor,        metolachlor, pretilachlor and propachlor; dinitroanilines, such        as, for example, oryzalin, pendimethalin and trifluralin;        diphenyl ethers, such as, for example, acifluorfen, bifenox,        fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen;        ureas, such as, for example, chlortoluron, diuron, fluometuron,        isoproturon, linuron and methabenzthiazuron; hydroxylamines,        such as, for example, alloxydim, clethodim, cycloxydim,        sethoxydim and tralkoxydim; imidazolinones, such as, for        example, imazethapyr, imazamethabenz, imazapyr and imazaquin;        nitriles, such as, for example, bromoxynil, dichlobenil and        ioxynil; oxyacetamides, such as, for example, mefenacet;        sulfonylureas, such as, for example, amidosulfuron,        bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron,        cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron,        pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and        tribenuron-methyl; thiocarbamates, such as, for example,        butylate, cycloate, di-allate, EPTC, esprocarb, molinate,        prosulfocarb, thiobencarb and triallate; triazines, such as, for        example, atrazine, cyanazine, simazine, simetryn, terbutryn and        terbutylazine; triazinones, such as, for example, hexazinone,        metamitron and metribuzin; others, such as, for example,        aminotriazole, benfuresate, bentazone, cinmethylin, clomazone,        clopyralid, difenzoquat, dithiopyr, ethofumesate,        fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate,        quinchlorac, quinmerac, sulphosate and tridiphane.

The active compound according to the invention can furthermore bepresent in its commercially available formulations and in the use forms,prepared from these formulations, as a mixture with synergistic agents.Synergistic agents are compounds which increase the action of the activecompounds without it being necessary for the synergistic agent added tobe active itself

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are used in a customary manner appropriate for the useform.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an outstanding residual action on wood andclay and by a stability to alkali on limed substrates.

The active compounds according to the invention have an action not onlyagainst plant and hygiene pests and pests of stored products, but alsoin the veterinary medicine sector against animal parasites(ectoparasites), such as hard ticks, soft ticks, mange mites, harvestmites, flies (biting and licking), parasitic fly larvae, lice, hair liceand fleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp, Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattrida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Omithodorus spp., Otabiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trmbicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

For example, they show an outstanding activity against Boophilusmicroplus and Lucilia cuprina.

The active compounds of the formula (I) according to the invention arealso suitable for combating arthropods which infest agriculturalproductive livestock such as, for example, cattle, sheep, goats, horses,pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geeseand bees, other pets, such as, for example, dogs, cats, cage birds andaquarium fish, and also so-called test animals, such as, for example,hamsters, guinea pigs, rats and mice. By combating these arthropodscases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey etc) should be diminished, so that more economicanimal husbandry is possible by use of the active compounds according tothe invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through process and suppositories, by parenteraladministration, such as, for example, by injections (intra-muscular,subcutaneous, intravenous, intraperitoneal etc), implants, by nasaladministration, by dermal use in the form, for example, of dipping orbathing, spraying, pouring on and spotting on, washing and powdering,and also with the aid of moulded articles containing the activecompound, such as collars, ear marks, tail marks, limb bands, halters,marking devices, etc.

When used for livestock, poultry, pets and the like, the activecompounds of the formula (I) can be used as formulations (for examplepowders, emulsions, compositions capable of flow) which comprise theactive compounds in an amount of 1 to 80% by weight, directly or after100 to 10,000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds of the formula Iaccording to the invention display a high insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned as examples and preferred butwithout being limited:

Beetles, such as

-   -   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,        Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium        pertinex, Ernobius mollis, Priobium carpini, Lyctus Brunneus,        Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus        pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus        spec., Tryptodendron spec, Apate monachus, Bostrychus capucins,        Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus        minutus.        Hymenopterans, such as    -   Sirex Juvencus, Urocerus gigas, Urocerus gigas taignus and        Urocerus augur.        Termites, such as    -   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes        indicola, Reticulitermes flavipes, Reticulitermes santonensis,        Reticuitermes lucifugus, Mastotermes darwiniensis, Zootermopsis        nevadensis and Coptotermes formosanus.        Bristle-Tails    -   such as Lepisma saccharina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products, andlacquers and paints.

Material to be preserved from insect damage which is quite particularlypreferred is wood and processed wood products.

Wood and processed wood products which can be protected by the agentsaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example: building timber, wooden beams,railway sleepers, bridge components, boat gangplanks, wooden vehicles,crates, pallets, containers, telegraph masts, wood lagging, woodenwindows and doors, plywood, chipboards, joinery or wood products usedquite generally in house construction or building joinery.

The active compounds can be used as such or in the form of concentratesor generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent,water repellant, optionally siccatives and UV stabilizers, and ifappropriate dyestuffs and pigments, as well as other processingauxiliaries.

The insecticidal compositions or concentrates used for preservation ofwood and derived timber products comprise the active compound accordingto the invention in a concentration of 0.0001 to 95% by weight, inparticular 0.001 to 60% by weight.

The amount of composition or concentrate employed depends on the natureand the occurrence of the insects and on the medium. The optimum amountemployed for the use can in each case be determined by a series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound basedon the material to be preserved.

The solvent and/or diluent used is an organochemical solvent or solventmixture and/or an oily or oil-like organochemical solvent or solventmixture of low volatility and/or a polar organochemical solvent orsolvent mixture and/or water and, if appropriate, an emulsifier and/orwetting agent.

Oily or oil-like solvents having an evaporation number above 35 and aflash point above 30° C., preferably above 45° C., are preferablyemployed as organochemical solvents. Corresponding mineral oils oraromatic fractions thereof or solvent mixtures containing mineral oil,preferably white spirit, petroleum and/or alkylbenzene, are used as suchwater-insoluble, oily and oil-like solvents of low volatility.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum or aromatics having a boiling rangefrom 160 to 280° C., terpentine oil and the like are advantageouslyemployed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are employed.

The organic oily or oil-like solvents of low volatility having anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., can be replaced in part by organochemical solvents of highor medium volatility, provided that the solvent mixture likewise has anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., and that the insecticide/fungicide mixture is soluble orcan be emulsified in this solvent mixture.

According to a preferred embodiment, some of the organochemical solventor solvent mixture is replaced by an aliphatic polar organochemicalsolvent or solvent mixture. Aliphatic organochemical solvents containinghydroxyl and/or ester and/or ether groups, such as, for example, glycolethers, esters or the like, are preferably used.

Organochemical binders which are the synthetic resins and/or bindingdrying oils which are water-dilutable and/or soluble or dispersible oremulsifiable in the organochemical solvents employed and are known perse, in particular binders consisting of or comprising an acrylate resin,a vinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenolic resin, hydrocarbon resin, such asindene-coumarone resin or silicone resin, drying plant and/or dryingoils and/or binders which dry by physical means and are based on anaturally occurring and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Inaddition, dyestuffs, pigments, water-repellant agents, odour correctantsand inhibitors or corrosion prevention agents and the like which areknown per se can be employed.

Preferably, according to the invention, the composition or concentratecomprises at least one alkyd resin or modified alkyd resin and/or onedrying plant oil as an organochemical binder. Alkyd resins having an oilcontent of more than 45% by weight, preferably 50 to 68% by weight, arepreferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether, or ketones, such as benzophenone orethylenebenzophenone.

Water in particular is also a possible solvent or diluent, ifappropriate mixed with one or more of the abovementioned organochemicalsolvents or diluents, emulsifiers and dispersing agents.

Particularly effective wood preservation is achieved by impregnationprocesses on a large industrial scale, for example vacuum, a doublevacuum or pressure processes.

If appropriate, the ready-to-use compositions can also comprise otherinsecticides, and if appropriate also one or more fungicides.

Possible additional admixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29268. The compounds mentioned in thisdocument are an express constituent of the present application.

Especially preferred admixing partners can be insecticides, such aschlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin,cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl butylcarbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example (I-1-a-1)

25.0 g (0.072 mol) of the compound according to Example (II-2) in 150 mlof anhydrous toluene are added dropwise to 18.5 g (0.165 mol) ofpotassium tert-butylate in 57 ml of anhydrous tetrahydrofuran (THF) atthe reflux temperature and the mixture is stirred under reflux for 1.5hours. For working up, 220 ml of water are added, the aqueous phase isseparated off, the toluene phase is extracted with 110 ml of water andthe aqueous phases are combined, washed with toluene and acidified withabout 26 ml of concentrated HCl at 10 to 20° C. The product is filteredoff with suction, washed, dried and washed by stirring in methyltert-butyl (MTB) ether/n-hexane.

-   -   Yield: 18.0 g (79% of theory), melting point: 159° C.

The following compounds of the formula (I-1-a) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE I (I-l-a)

Melting Example point Iso- No. X Y Z A B °C. mer I-1-a-2 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— >220 β I-1-a-3 Cl Cl Cl—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-4 CH₃ Cl CH₃—(CH₂)₂—CHCH₃—(CH₂)₂ >220 β I-1-a-5 CH₃ CH₃ CH₃ —(CH₂)₂—O—(CH₂)₂— >220I-1-a-6 CH₃ Br Cl —(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-7 Br CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— 221 β I-1-a-8 Cl —O—CF₂—O— —(CH₂)₂—CHCH₃—(CH₂)₂—180 β dec. I-1-a-9 Br —(CH₂)₃— —(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-10 ClCH₃ Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— 208 β I-1-a-11 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-12 CH₃ Br CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—208 β I-1-a-13 Cl Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— 206 β I-1-a-14 Cl Br CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β I-1-a-15 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— >220 β

Example (I-1-b-1)

1.13 ml (0.015 mol) of acetyl chloride in 5 ml of absolute methylenechloride are added to 4.5 g (0.015 mol) of the compound according toExample (I-1-a-1) and 2.1 ml (15 mmol) of triethylamine in 70 ml ofabsolute methylene chloride at 0 to 10° C. The mixture is stirred atroom temperature until, according to monitoring by thin layerchromatography, the reaction has ended. For working up, the mixture iswashed twice with 50 ml of 0.5 N sodium hydroxide solution, dried overmagnesium sulphate and evaporated. The crude product is recrystallizedfrom MTB ether/n-hexane.

-   -   Yield: 3.4 g (66% of theory), melting point: 209° C.

The following compounds of the formula (I-b-1) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE 2 (I-1-b)

Melting Example point Iso- No. X Y Z A B R¹ ° C. mer I-1-b-2 CH₃ CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 208 β I-1-b-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 152 β I-1-b-4 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇ 194 α* I-1-b-5 Cl Cl Cl—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ >220 β I-1-b-6 CH₃ CH₃ CH₃—(CH₂)₂—O-(CH₂)₂— i-C₃H₇ >220 — I-1-b-7 CH₃ Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—i-C₃H₇ 213 β I-1-b-8 CH₃ Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— i-C₄H₉ 208 βI-1-b-9 Cl Br CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 187 β I-1-b-10 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 151 β 1-1-b-11 Br CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉ 217 β I-1-b-12 Br CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ 198 β I-1-b-13 CH₃ Br Cl—(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉ 194 β I-1-b-14 CH₃ Br CI—(CH₂)₂—CHCH₃—(CH₂)₂— i-C₃H₇ >220 β *The α isomers were separated offfrom the isomer mixtures as a secondary component by chromatographicseparation.

Example (I-1-c-1)

1.5 ml (15 mmol) of ethyl chloroformate in 5 ml of absolute methylenechloride are added dropwise to 4.5 g (0.015 mol) of the compoundaccording to Example (I-1-a-1) and 2.1 ml of triethylamine in 70 ml ofabsolute methylene chloride at 0 to 10° C. and the mixture is stirred atroom temperature until, according to monitoring by thin layerchromatography, the reaction has ended. For working up, the mixture iswashed twice with 50 ml of 0.5 N sodium hydroxide solution, dried overmagnesium sulphate and evaporated.

-   -   Yield: 3.3 g (59% of theory), melting point: 193° C.

The following compounds of the formula (I-1-c) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE 3 (I-1-c)

Melting Example point Iso- No. X Y Z A B L M R² ° C. mer I-1-c-2 CH₃ CH₃CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— O O i-C₄H₉ 119 β I-1-c-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— O O i-C₄H₉ 207 α* I-1-c-4 CH₃ Br Cl—(CH₂)₂—CHCH₃—(CH₂)₂— O O C₂H₅ >220 β I-1-c-5 CH₃ CH₃ CH₃—(CH₂)₂—O—(CH₂)₂— O O i-C₄H₉ 205 — I-1-c-6 Cl Cl Cl—(CH₂)₂—CHCH₃—(CH₂)₂— O O i-C₄H₉ 215 β I-1-c-7 CH₃ Cl CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— O O C₂H₅ 210 β I-1-c-8 CH₃ Cl CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— O O i-C₄H₉ 214 β I-I-c-9 Cl Br CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— O O C₂H₅ 223 β *The α isomers were separated offfrom the isomer mixtures as secondary products by chromatographicseparation.

Example II-1

17.5 g of the compound according to Example (XXIX-1) in about 100 ml ofmethylene chloride are cautiously added dropwise to 30.3 g (0.308 mol)of concentrated sulphuric acid at 30 to 40° C. and the mixture isstirred at this a temperature for 2 hours. 41 ml of absolute methanolare then added dropwise such that an internal temperature of about 40°C. is established, and the mixture is stirred at 40 to 70° C. for afurther 6 hours.

For working up, the mixture is poured onto 0.29 kg of ice, extractedwith methylene chloride, washed with aqueous sodium bicarbonatesolution, dried and evaporated. The crude product is purified by columnchromatography over silica gel using the mobile phase methylenechloride/ethyl acetate 2:1.

-   -   Yield: 13.1 g (67% of theory), melting point: 147° C.

Example (II-2)

40.9 g (0.23 mol) of 2,4,5-trimethylphenylacetic acid and 33.6 ml (0.461mol) of thionyl chloride are stirred at room temperature for 30 minutesand then at 50° C. until the evolution of gas has ended. Excess thionylchloride is removed at 50° C. in vacuo. 50 ml of absolute toluene arethen added and the mixture is evaporated again. The residue is taken upin 100 ml of absolute THF (solution 1).

Solution 1 is added to 47.9 g of methylcis-4-methylcyclohexylamine-1-carboxylate and 64.6 ml (0.460 mol) oftriethylamine in 600 ml of absolute THF at 0 to 10° C. and the mixtureis then stirred at room temperature for 1 hour. It is then filtered withsuction, washed with absolute THF and evaporated. The residue is takenup in methylene chloride and the mixture is washed with 0.5 N HCl, driedand evaporated. The crude product is purified by column chromatographyover silica gel using methylene chloride/ethyl acetate 7:1.

-   -   Yield: 25 g (32% of theory), melting point: 158° C.

The following compounds of the formula (II) are prepared analogously toExamples (II-1) and (II-2) and in accordance with the generalinformation on the preparation.

TABLE 4 (II)

Melting Example point Iso- No. X Y Z A B R⁸ ° C. mer II-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃— CH₃ 161 β (CH₂)₂— II-4 CH₃ Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 192 β II-5 Cl Cl Cl —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 194 β II-6 Cl Br CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 196 β II-7 Cl CN CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃163 β II-8 Br Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 170 β II-9 Br CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 158 β II-10 CH₃ Br Cl —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 197 β II-11 F Cl OCH₃ i-C₃H₇ CH₃ CH₃ 109- — 111 II-12 Cl —O—CF₂—O——(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 164 β II-13 Cl Cl CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂—CH₃ 189 β II-14 CH₃ Br CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 171 β II-15 CH₃ ClCH₃ —(CH₂)₂—CHOCH₃— CH₃ 173 β (CH₂)₂— II-16 CH₃ Br CH₃ —(CH₂)₂—CHOCH₃—CH₃ 183 β (CH₂)₂— II-17 Br CH₃ CH₃ —(CH₂)₂—CHOCH₃— CH₃ 142 β (CH₂)₂—II-18 Cl Br CH₃ —(CH₂)₂—CHOCH₃— CH₃ β (CH₂)₂— II-19 CH₃ CH₃ CH₃ CH₃ CH₃CH₃ 159 — II-20 CH₃ CH₃ CH₃ i-C₃H₇ CH₃ CH₃ II-21 Cl CH₃ Cl—(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 150 β II-22 Br CH₃ Cl —(CH₂)₂—CHOCH₃— CH₃ β(CH₂)₂— II-23 Cl Cl F —(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 171 β II-24 Cl Cl F—(CH₂)₂—CHOCH₃— CH₃ 182 β (CH₂)₂— II-25 Br —(CH₂)₃——(CH₂)₂—CHCH₃—(CH₂)₂— CH₃ 168 β

Example (XXIX-1)

Starting from 17.8 g of 2,4,5-trimethylphenylacetic acid, solution 1 isprepared as in Example (II-2).

Solution 1 is added dropwise to 16.8 g of1-amino-tetrahydropyran-1-carboxylic acid nitrile (70% pure) and 16.8 ml(0.12 mol) of triethylamine in 150 ml of absolute THF at 0 to 10° C. andthe mixture is stirred at room temperature for a further hour. It isthen evaporated, the residue is taken up in methylene chloride and themixture is washed with 0.5 N HCl, dried and evaporated. The crudeproduct is recrystallized from MTB ether/n-hexane.

-   -   Yield: 17.5 g (61% of theory), melting point: 156° C.

Example (I-2-a-1)

8.42 g (75 mmol) of potassium tert-butylate are initially introducedinto 50 ml of dimethylformamide, a solution of 16.6 g (50 mmol) of1-ethyloxycarbonylcyclohexyl 2,4,5-trimethyl-phenylacetate according toExample (III-1) in 50 ml of dimethylformamide is added dropwise at 0 to10° C. and the mixture is stirred overnight at room temperature.

For working up, the reaction mixture is added dropwise in 500 ml ofice-cold 1 N HCl and the product which has precipitated out is filteredoff with suction, washed with water and dried in a vacuum dryingcabinet. For further purification, the crude product is boiled upfurther with n-hexane/acetone.

-   -   Yield: 9.2 g (64% of theory) of melting point: 209-212° C.

The following compounds of the formula (I-2-a) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE 5 (I-2-a)

Melting Example point No. X Y Z A B ° C. I-2-a-2 CH₃ CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— 190- 193 I-2-a-3 CH₃ CH₃ CH₃—(CH₂)₂—CHOCH₃—(CH₂)₂— 167- 170 1-2-a-4 CH₃ Cl CH₃ —(CH₂)₅— 241- 2431-2-a-5 Cl Cl Cl —(CH₂)₅— 288 I-2-a-6 CH₃ Br Cl —(CH₂)₅— 242- 243I-2-a-7 CH₃ Br Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— 153- 154 I-2-a-8 Cl Br CH₃—(CH₂)₅— 232- 233 I-2-a-9 Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— 167- 177I-2-a-10 F Cl OCH₃ CH₃ CH₃ 118- 120 I-2-a-11 Cl —O—CF₂—O— —(CH₂)₅— 247I-2-a-12 Cl CN CH₃ —(CH₂)₅— 220- 225

Example (I-2-b-1)

2.86 g (10 mmol) of the compound according to Example I-2-a-1 areinitially introduced into 40 ml of methylene chloride, 1.52 g (15 mmol)of triethylamine are added, a solution of 1.57 g (13 mmol) of pivaloylchloride in 40 ml of methylene chloride is added dropwise, while coolingwith ice, and the mixture is subsequently stirred at room temperaturefor 1 to 2 hours. For working up, the mixture is washed successivelywith 10% strength citric acid, 1N NaOH and NaCl solution and the organicphase is dried over MgSO₄ and evaporated. For further purification, thecrude product is stirred further with a little petroleum ether.

-   -   Yield: 3.0 g (81% of theory) of melting point: 128-132° C.

The following compounds of the formula (I-2-b) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE 6 (I-2-b)

Melting Example point No. X Y Z A B R¹ ° C. I-2-b-2 CH₃ CH₃ CH₃ —(CH₂)₅—i-C₃H₇— 85-88 I-2-b-3 CH₃ CH₃ CH₃ —(CH₂)₂—CHCH₃—(CH₂)₂— t-C₄H₉— 139-143I-2-b-4 CH₃ CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 114-118 I-2-b-5 CH₃CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 125-129 I-2-b-6 Cl Cl Cl —(CH₂)₅—t-C₄H₉— 149 I-2-b-7 Cl Cl Cl —(CH₂)₅— t-C₄H₉—CH₂— 133 I-2-b-8 CH₃ Br Cl—(CH₂)₅— t-C₄H₉—CH₂— 146-147 I-2-b-9 CH₃ Br Cl —(CH₂)₅— t-C₄H₉— 168I-2-b-10 CH₃ Br Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇— 132-133 I-2-b-11 CH₃Br Cl —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 145-149 I-2-b-12 CH₃ Cl CH₃—(CH₂)₅— t-C₄H₉— 160 I-2-b-13 CH₃ Cl CH₃ —(CH₂)₅— t-C₄H₉—CH₂— 157I-2-b-14 Cl Br CH₃ —(CH₂)₅— t-C₄H₉—CH₂— 161-162 I-2-b-15 Cl Br CH₃—(CH₂)₅— t-C₄H₉— 170 I-2-b-16 Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— i-C₃H₇—98-99 I-2-b-17 Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— t-C₄H₉— 139-140 I-2-b-18Cl —O—CF₂—O— —(CH₂)₅— t-C₄H₉— 125

Example (III-1)

8.9 g (50 mmol) of 2,4,5-trimethyl-phenylacetic acid are initiallyintroduced into 50 ml of toluene, 11.9 g (100 mmol) of thionyl chlorideare added and the mixture is stirred at 80° C. until the evolution ofhydrogen chloride has ended and is then evaporated. The crude acidchloride is boiled in 50 ml of toluene together with 8.6 g (50 mmol) ofethyl 1-hydroxy-cyclohexanecarboxylate overnight and the mixture is thenevaporated.

-   -   Yield: 18.6 g (quantitative) of 1-ethoxycarbonyl-cyclohexyl        2,4,6-trimethylphenylacetate as a colourless oil.

The following compounds of the formula (III) are obtained analogouslyand in accordance with the general instructions for preparation:

TABLE 7 (III)

Melting Example point No. X Y Z A B R⁸ ° C. III-2 CH₃ CH₃ CH₃—(CH₂)₂—CHCH₃—(CH₂)₂— C₂H₅ oil III-3 CH₃ CH₃ CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂—C₂H₅ oil III-4 CH₃ Cl CH₃ —(CH₂)₅— C₂H₅ oil III-5 Cl Cl Cl —(CH₂)₅— C₂H₅oil III-6 CH₃ Br Cl —(CH₂)₅— C₂H₅ oil III-7 CH₃ Br Cl—(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅ oil III-8 Cl Br CH₃ —(CH₂)₅— C₂H₅ oil III-9Cl Br CH₃ —(CH₂)₂—CHOCH₃—(CH₂)₂— C₂H₅ oil III-10 F Cl OCH₃ CH₃ CH₃ C₂H₅oil III-11 Cl —O—CF₂—O— —(CH₂)₅— C₂H₅ oil III-12 Cl CN CH₃ —(CH₂)₅— C₂H₅oil

Example (I-3-a-1)

26.0 g (60.7 mmol) of the compound according to Example (IV-1) areheated under reflux with 55 ml of trifluoroacetic acid in 110 ml oftoluene for 3 hours. Excess trifluoroacetic acid is removed in vacuo,400 ml of water and 120 ml of MTB ether are added to the residue and thepH is brought to 14 with NaOH. The mixture is extracted twice with MTBether and the aqueous phase is acidified with concentrated HCl andextracted 3 times with MTB ether. The organic phases are dried andconcentrated. Yield 8.8 g (52% of theory), melting point 160 to 162° C.

Example (I-3-b-1)

Preparation

1.0 g (3.6 mmol) of the compound according to Example I-3-a-1 areinitially introduced into 15 ml of absolute methylene chloride, and 0.75ml of triethylamine is added. A solution of 0.82 g (4.68 mmol) of6-chloronicotinyl chloride in 3 ml of absolute methylene chloride isadded dropwise, while cooling with ice. The mixture is stirred at roomtemperature for 2 hours. It is washed twice with 10% strength citricacid and the combined aqueous phases are extracted with methylenechloride. The combined organic phases are washed twice with 1 N NaOH andthe aqueous alkaline phases are extracted with methylene chloride.Finally, the combined organic phases are dried and concentrated and theresidue is stirred with petroleum ether. Yield 1.37 g (91% of theory),melting point 123 to 126° C.

The compounds of the formula I-3-b listed in the following table wereprepared analogously to Example I-3-b-1 and in accordance with thegeneral description.

I-3-b

Example No. X Y Z A B R¹ Melting point ° C. I-3-b-2 CH₃ CH₃ CH₃ C₂H₅ CH₃t-C₄H₉ oil I-3-b-3 CH₃ CH₃ CH₃ C₂H₅ CH₃ Cyclopropyl oil I-3-b-4 CH₃ CH₃CH₃ C₂H₅ CH₃ Cl—CH₂—C(CH₃)₂ oil

Example (I-3-c-1)

Preparation:

1.0 g (3.6 mmol) of the compound according to Example I-3-a-1 areinitially introduced into 15 ml of absolute methylene chloride, and 0.75ml (1.5 equivalents) of triethylamine is added. A solution of 0.61 ml(0.64 g; 4.68 mmol) of isobutyl 6-chloroformate in 3 ml of absolutemethylene chloride is added dropwise, while cooling with ice. Themixture is stirred at room temperature for 2 hours. It is washed twicewith 10% strength citric acid and the combined aqueous phases areextracted with methylene chloride. The combined organic phases arewashed twice with 1 N NaOH and the aqueous alkaline phases are extractedwith methylene chloride. Finally, the combined organic phases are driedand concentrated.

-   -   Yield 1.32 g (97% of theory), oil

¹H-NMR (400 MHz, DMSO):

-   -   δ═0.60-0.70 m, 6H, CH(CH ₃)₂        -   1.00-1.05 m, 3H, CH₂CH ₃        -   1.50-1.60 m, 1H, CH(CH₃)₂        -   1.70-1.76 d, 3H, C(CH ₃)        -   1.90-2.02 m, 2H, CH ₂CH₃        -   2.05-2.20 m, 9H, ArCH ₃        -   3.65-3.72 m, 2H, OCH ₂        -   6.75-6.80 d, 1H, ortho Ar—H        -   7.01 s, 1H, meta Ar—H

Example (I-3-c-2)

The compound of the formula (I-3-c-2) was obtained analogously toExample (I-3-c-1) as an oil:

Example (IV-1)

A: 25 g (98 mmol) of the compound of the formula (XXXII-1)

-   -   1 drop of dimethylformamide are stirred with 17.5 g (147 mmol)        of thionyl chloride in 100 ml of toluene at room temperature for        5 minutes and then at 100° C. until the evolution of gas has        ended. Volatile constituents are removed under a high vacuum.        B: 72 ml (118 mmol) of butyllithium (1.6 M) are added dropwise        to 18 ml (130 mmol) of diisopropylamine in 100 ml of THF, while        cooling with ice, and the mixture is stirred at this temperature        for a further 15 minutes. 18.8 g (108 mmol) of the compound        according to Example (XXIV-3), dissolved in 40 ml of THF, are        then added dropwise at 0° C. and the mixture is stirred at this        temperature for 30 minutes. The acid chloride prepared according        to A, dissolved in 40 ml of THF, is then added dropwise at 0° C.        and the mixture is stirred at room temperature for 1 hour. 350        ml of MTB ether and a few drops of water are then added and the        mixture is extracted twice with 10% strength ammonium chloride        solution, dried and concentrated. The crude product (40 g) is        purified by column chromatography (mobile phase        cyclohexane/ethyl acetate 10/1). Yield 27.0 g (64% of theory),        oil.

¹H-NMR (CDCl₃, 400 MHz):

-   -   δ═0.80-0.95 m, 3H, CH₂CH₃        -   1.42 s, 3H, C—CH ₃        -   1.65-2.05 m, 2H, CH ₂CH₃        -   2.15-2.35 m, 9H, ArCH ₃        -   3.10-3.45 m, 2H, SCH ₂        -   3.70-3.80 m, 6H, OCH ₃        -   6.70-7.30 m, 6H, Ar—H

Example (I-4-a-1)

6.7 g (30 mmol) of 2-(2,4,5-trimethylphenyl)-chlorocarbonylketene areheated at 200° C. with 4.3 g (30 mmol) of4,5-dihydro-2,2,5,5-tetramethyl-3-(2H)-furanone for 4 hours. Aftercolumn chromatography over silica gel using toluene/ethanol 20:1 as themobile phase, 4.6 g (Δ 46% of theory) of melting point: 182-184° C. areobtained.

The following compounds of the formula (I-4-a) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE 8 (I-4-a)

Melting Example point No. X Y Z A D ° C. I-4-a-2 CH₃ CH₃ CH₃ —CO—(CH₂)₃—134-137 I-4-a-3 CH₃ CH₃ CH₃ CH₃ 4-F-Phenyl 216-218 I-4-a-4 CH₃ CH₃ CH₃CH₃ 2-Pyridyl 130-132 I-4-a-5 CH₃ CH₃ CH₃ CH₃

65-68 I-4-a-6 CH₃ CH₃ CH₃ CH₃ 4-Cl- 192-194 Phenyl-

Example (I-4-b-1)

2.5 g (7.5 mmol) of the compound (I-4-a-1) are initially introduced into25 ml of ethyl acetate, 0.75 g of triethylamine is added, and 0.6 g ofacetyl chloride in 20 ml of ethyl acetate is added dropwise at 0° C. Themixture is stirred at room temperature for 20 hours, the precipitate isseparated off and the product is washed twice with 50 ml ofhalf-concentrated sodium chloride solution, dried over sodium sulphateand evaporated in vacuo. The residue is chromatographed over silica gelusing toluene/acetone 50:1.

-   -   Yield: 0.8 g (Δ 29% of theory) of melting point: 143-144° C.

The compounds of the formula I-4-b listed in the following table wereprepared analogously to Example I-4-b-1 and in accordance with thegeneral information on the preparation:

TABLE 9 (I-4-b)

Melting point: [° C.] σ. Example ¹H-NMR (CDCl₃): δ No. X Y Z A D R¹[ppm] I-4-b-2 CH₃ CH₃ CH₃ CH₃ 4-F-Phenyl CH₃ 141-143 I-4-b-3 CH₃ CH₃ CH₃CH₃ 2-Pyridyl CH₃ 135-136 I-4-b-4 CH₃ CH₃ CH₃ CH₃ 2-PyridylC(CH₃)—(CH₂OCH₃)₂ 8.68(1H, d), 7.98(1H, d), 7.80(1H, t), 2.33(3H, s),2.23(3H, s), 2.20(3H, s), 2.15(3H, s) I-4-b-5 CH₃ CH₃ CH₃ CH₃

CH₃ 137-139

Example (I-4-c-1)

1.7 g (5 mmol) of the compound (I-4-a-3) are initially introduced into20 ml of ethyl acetate, 0.5 g (5 mmol) of triethylamine is added, and0.5 g (5 mmol) of methyl chloroformate in 5 ml of ethyl acetate is addeddropwise at 0° C. The mixture is stirred at room temperature for 20hours, the precipitate is separated off and the product is washed twicewith 50 ml of half-concentrated sodium chloride solution, dried oversodium sulphate and evaporated in vacuo. The residue is chromatographedover silica gel using toluene/acetone 30/1. Yield 1.0 g (51% of theory)of melting point 144 to 146° C.

The following compounds of the formula (I-4-c) are obtained analogouslyand in accordance with the general information on the preparation:

TABLE 10 (I-4-c)

Example Melting No. X Y Z A D R² L M point ° C. I-4-c-2 CH₃ CH₃ CH₃ CH₃2-Pyridyl CH₃ O O 160-162 I-4-c-3 CH₃ CH₃ CH₃ CH₃ 2-Pyridyl CH(CH₃)—C₂H₅O O 107-109

Example (I-5-a-1)

2.2 g (10 mmol) of 2-(2,4,5-trimethylphenyl)-chloro-carbonylketene areheated at 50° C. with 1.6 g (10 mmol) of 4-fluorothiobenzamide in 80 mlof toluene for 6 hours. The precipitate is separated off, washed withcyclohexane and dried. 2.8 g (82% of theory) of melting point 215 to216° C. are obtained.

Example (XXIII-1)

247 g (1.162 mol) of the compound according to Example (XXIV-1) (75%pure) are added dropwise to a mixture of 100 g (1.785 mol) of KOH in 130ml of water and 260 ml of methanol at room temperature and the mixtureis heated under reflux for 5 hours. After cooling, it is diluted with300 ml of water and extracted with ethyl acetate. The aqueous phase isacidified with half-concentrated hydrochloric acid and the precipitateis filtered off with suction and dried.

-   -   Yield: 77 g (45% of theory), melting point: 119-121° C.

Example (XXIII-2)

2,4,5-Trichloro-phenylacetic acid, melting point: 112-115° C., isobtained analogously to Example (XXII-1)Preparation of 2,4,5-trimethyl-phenylacetic Acid

Me═CH₃

Example (XXIII-3)

286 g (1.4 mol) of 66% pure 1,2,4,5-tetramethylbenzene are dissolved in563 ml of carbon tetrachloride, and 27.5 g (0.15 mol) ofN-bromosuccinimide and 0.4 g of benzoyl chloride are introduced insuccession at room temperature. The mixture is heated to 80° C. and 248g (1.39 mol) of N-bromosuccinimide are added in portions. Thereafter,the mixture is subsequently stirred at 80° C. for a further 30 minutesand is then cooled to room temperature. The solid is filtered off withsuction and the solvent is stripped off under 20 mbar via a solidsbridge. The residue is then distilled under a high vacuum and 226 g (66%of theory) of 2,4,5-trimethylbenzyl bromide having a boiling point of95° C. under 0.05 mbar and a purity of 86% are obtained.

A solution of 226 g (0.91 mol) of 2,4,5-trimethyl-benzyl bromide (86%pure) in 94 ml of toluene is added dropwise to a solution of 57 g (1.16mol) of sodium cyanide in 63 ml of water and 0.6 g of Aliquat 336 at 60to 80° C., and the mixture is then subsequently stirred at 80° C. for 4hours. After cooling to room temperature, the phases are separated andthe organic phase is washed twice with water and twice with saturatedNaCl solution, dried and concentrated. After distillation, 103 g (70%)of 2,4,5-trimethyl-benzyl cyanide having a purity of 99% and a boilingpoint of 120° C. under 0.2 mbar are obtained.

2118 ml of concentrated sulphuric acid are added dropwise to 2662 ml ofwater at room temperature and the solution is heated to 90° C. 355 g(2.23 mol) of 2,4,5-trimethyl-benzyl cyanide are metered into thehalf-concentrated sulphuric acid at this temperature and the mixture issubsequently stirred at 100° C. for 8 hours. After cooling, the reactionmixture is poured into ice-water, while stirring vigorously, andfiltered with suction. The solid is washed several times with water andthen with petroleum ether and dried. 358 g (90% of theory) of2,4,5-trimethylphenylacetic acid having a melting point of 123-125° C.are obtained.

The novel phenyl acetic acids of formula (XXIII) listed in the followingTable 11 were prepared analogously to Examples (XXIII-1) and (XXIII-3)and in accordance with the general information on the preparation:

TABLE 11 (XXIII)

melting point Example No. X Y Z ° C. XXIII-4 Cl Br CH₃ 118-120 XXIII-5Cl CN CH₃ 164-169 XXIII-6 Br CH₃ Cl 123-125 XXIII-7 Br CH₃ CH₃ 122XXIII-8 CH₃ Br Cl 148-150 XXIII-9 F Cl OCH₃ XXIII-10 Cl —O—CF₂—O—115-119 XXIII-11 Cl Cl CH₃ 101 XXIII-12 CH₃ Br CH₃ 141 XXIII-13 Cl CH₃Cl 112 XXIII-14 Br —(CH₂)₃— 143 XXIII-15 Cl Cl F 118

The compounds of formula (XXIII) are novel excepted the compounds inwhich X, Y, Z═CH₃ and in which X, Y, Z═Cl.

Example (XXIV-3)

35 g (0.143 mol) of methyl 2-chloro-4-bromo-5-methylphenylacetate and 31g of CuCN are heated under reflux in 350 ml of dimethylformamide for 1day. The solvent is stripped of under vacuum, the residue is partitionedbetween water and tert. butyl-methylether, the organic phase is driedand evaporated.

-   -   Yield: 18 g.

The novel phenyl acetic acid esters of formula (XXIV) listed in Table 12were prepared analogously to Example (XXIV).

TABLE 12 (XXIV)

Example No. X Y Z physic. constant XXIV-4 Cl Br CH₃ mp.: 41-43° C.XXIV-5 Br CH₃ Cl mp.: 37-38° C. XXIV-6 Br CH₃ CH₃ Kp_(0.03 mbar)89-91°C. XXIV-7 CH₃ Br Cl Kp_(0.07 mbar)107-110° C. XXIV-8 Cl —O—CF₂—O— oilXXIV-9 Cl Cl CH₃ Kp_(0.4 mbar)89-91° C. XXIV-10 CH₃ Br CH₃Kp_(0.03 mbar)96-98° C. XXIV-11 Br —(CH₂)₃— Kp_(0.2 mbar)130-135° C.

The compounds of formula (XXIV) are novel except the compound in whichX, Y, Z═CH₃ and in which X, Y, Z═Cl.

Example (XXIV-1)

700 ml of a 30% strength methanolic solution of sodium methylate areadded dropwise to a solution of 347 g (0.948 mol) of the compoundaccording to Example (XXV-1) (74.3% pure) in 410 ml of methanol at roomtemperature, the mixture is heated under reflux for 5 hours and cooledto room temperature and 0.110 ml of concentrated sulphuric acid areadded dropwise. The mixture is boiled under reflux for 1 hour, themethanol is distilled off and the solid residue is taken up in water.The organic phase is separated off and the aqueous phase is extractedtwice with 1.5 l of methylene chloride. The combined organic phases aredried over Na₂SO₄ and concentrated.

-   -   Yield: 247 g of a dark oil Δ 92% of theory having a content of        75% (gas chromatography).

Example (XXIV-2)

Methyl 2,4,5-trichloro-phenylacetate is obtained analogously to Example(XXIV-1) as a dark oil in a yield of 95% of theory and a purity of 80%(gas chromatography).

Example (XXV-1)

2205 g (22.7 mol) of 1,1-dichloroethene are added dropwise to athoroughly cooled mixture of 229.7 g (2.272 mol) of tert-butyl nitriteand 254.8 g (1.775 mol) of anhydrous copper(II) chloride in 990 ml ofanhydrous acetonitrile, the mixture being kept at below 30° C. A mixtureof 232 g (1.49 mol) of 4-chloro-2,5-dimethylaniline and 1500 ml ofanhydrous acetonitrile is then added dropwise at a temperature of below30° C. The mixture is stirred at room temperature until the evolution ofgas has ended and is then poured cautiously into 6 l of 20% strength HCland extracted several times with a total of 6 l of methyl tert-butylether (MTBE). The combined organic phases are washed with 20% strengthHCl, dried and concentrated. The oil which remains is rectified.

Yield: 347 g of dark oil Δ 63% of theory having a content of 74% (gaschromatography).

Example (XXV-2)

2-(2,4,5-Trichlorophenyl)-1,1,1-trichloroethane was obtained analogouslyto Example (XXV-1) in the form of a dark oil in a yield of 81% of theorywith a content of 78%.

The 1,1,1-trichloro-2-phenyl-ethanes of formula (XXV) listed in Table 13were prepared analogously to Example (XXV-1)

TABLE 13 (XXV)

Example No. X Y Z physic. constant XXV-3 Cl Br CH₃ mp.: 82-84° C. XXV-4Br CH₃ Cl oil* XXV-5 Br CH₃ CH₃ oil* XXV-6 CH₃ Br Cl oil* XXV-7 Cl—O—CF₂—O— oil* XXV-8 Cl Cl CH₃ mp.: 70-72° C. XXV-9 CH₃ Br CH₃ oil*XXV-10 Br —(CH₂)₃— oil 

The oils were used without further purification for the preparation ofthe compounds of formula (XXIV). The compounds of formula (XXV) arenovel except the compound in which X, Y, Z═Cl.

Synthesis of 2,4,5-trimethylphenylcarbonylketene

Methyl 2,4,5-trimethylphenylacetate

100 g (0.56 mol) of 2,4,5-trimethylphenylacetic acid were dissolved in230 ml of methanol, 6 ml of concentrated hydrochloric acid were addedand the mixture was heated under reflux for 10 hours. It was then cooledto room temperature and the methanol was removed in vacuo. The residuewas stirred into a solution of 53 g of sodium carbonate, dissolved in260 ml of water, and the organic phase was taken up in 200 ml oftoluene. The organic phase was separated off, dried and concentrated andthe residue was distilled. 48.6 g of methyl 2,4,5-trimethylphenylacetatehaving a boiling point of 86° C. under 0.2 mbar were obtained.Dimethyl 2-(2,4,5-trimethylphenyl)-malonate

18.6 g (0.62 mol, 80% pure) of sodium hydride were initially introducedinto 384 ml of dimethyl carbonate and the mixture was heated to about80° C. 48 g (0.25 mol) of methyl 2,4,5-trimethylphenylacetate, dissolvedin 100 ml of dimethyl carbonate, were then added dropwise and themixture was heated under reflux for 4 hours. It was cooled to roomtemperature, the excess sodium hydride was destroyed with ethanol andthe mixture was then poured into 1500 ml of ice-water. A pH of 4 to 5was established with 6 N hydrochloric acid and the organic phase wastaken up in toluene. The organic phase was separated off, dried andconcentrated and the residue was employed in the next stage withoutfurther purification. 51.6 g of dimethyl2-(2,4,5-trimethylphenyl)-malonate were obtained as an oil.

¹H-NMR (CDCl₃): δ=7.12 (s, 1H); 6.98 (s, 1H); 4.84 (s, 1H); 3.75 (s,6H); 2.27 (s, 3H); 2.23 (s, 3H); 2.21 ppm (s, 3H).2-(2,4,5-Trimethylphenyl)-malonic Acid

51.6 g (0.21 mol) of dimethyl 2-(2,4,5-trimethylphenyl)-malonate wereadded dropwise to a mixture of 180 ml of methanol and 38.1 g (0.68 mol)of potassium hydroxide, dissolved in 92 ml of water, at roomtemperature. The mixture was then heated under reflux for 5 hours andthen cooled to room temperature again and concentrated.

The residue was stirred into ice-water and the mixture was washed with alittle toluene. The aqueous solution was acidified to a pH of 1 withconcentrated hydrochloric acid, while cooling with ice, and theprecipitate was filtered off with suction and dried. 30.3 g of2-(2,4,5-trimethylphenyl)-malonic acid were obtained.

¹H-NMR (d₆-DMSO): δ=7.03 (s, 1H); 6.95 (s, 1H); 4.66 (s, 1H); 2.17 (s,3H); 2.16 ppm (s, 6H).2,4,5-Trimethylphenylchlorocarbonyl Ketene

30 g of 2-(2,4,5-trimethylphenyl)-malonic acid were suspended in 60 mlof toluene at 50 to 60° C. and 62.5 ml of thionyl chloride were addeddropwise. The mixture was then heated at 90 to 100° C. for 15 hours. Itwas then cooled, the volatile constituents were driven off with an inertgas and the excess thionyl chloride was distilled off. 30.6 g of2,4,5-trimethylphenylchlorocarbonyl ketene were isolated as the residue.

¹H-NMR (CDCl₃): δ═7.07 (s, 2H); 2.27 (s, 3H); 2.22 (s, 3H); 2.21 ppm (s,3H).

USE EXAMPLES Example A

Phaedon Larvae Test

-   -   Solvent: 7 parts by weight of dimethylformamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae), as long asthe leaves are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the beetle larvae have been killed; 0% means thatnone of the beetle larvae have been killed.

In this test, for example, the compounds according to PreparationExamples I-4-b-1 and I-4-a-4 caused a destruction of 100% after 7 daysat an active concentration of, for example, 0.1%.

Example B

Plutella Test

-   -   Solvent: 7 parts by weight of dimethylformamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellamaculipennis) while the leaves are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example, the compounds according to PreparationExamples I-1-a-1, I-1-b-2, I-1-c-1, I-4-a-3,1-4-a-1, I-4-b-1 and I-4-a-4caused a destruction of 100% after 7 days at an active compoundconcentration of, for example, 0.1%.

Example C

Spodoptera Test

-   -   Solvent: 7 parts by weight of dimethylformamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the owlet moth (Spodoptera frugiperda)while the leaves are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example, the compounds according to PreparationExamples I-1-a-1, I-1-b-2, I-4-a-3,1-4-a-1,1-4-b-1 and I-4-a-4 caused adestruction of 100% after 7 days at an active compound concentration of,for example, 0.1%.

Example D

Nephotettix Test

-   -   Solvent: 7 parts by weight of dimethylformamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryza sativa) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the rice green leafhopper (Nephotettixcincticeps) while the seedlings are still moist.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example, the compounds according to PreparationExamples I-2-a-2, I-2-a-3, I-2-b-4, I-2-b-5, I-1-a-1, I-1-b-2, I1-c-1,I-1-b-1, I-1-b-3, I-1-c-2, I-1-c-3, I-4-a-3 and I-4-a-4 caused adestruction of 100% after 6 days at an active compound concentration of,for example, 0.1%.

Example E

Myzus Test

-   -   Solvent: 7 parts by weight of dimethylformamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which are heavily infested by thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of the active compound of the desired concentration.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example, the compounds according to PreparationExamples I-2-a-1, I-2-b-4, I-1-b-2, I-1-b-3, I-1-c-2 and I-4-a-4 causeda destruction of 100% after 6 days at an active compound concentrationof, for example, 0.1%.

Example F

Tetranychus Test (OP-Resistant/Dipping Treatment)

-   -   Solvent: 7 parts by weight of dimethylformamide    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by thetwo-spotted spider mite (Tetranychus urticae) are treated by beingdipped into the preparation of the active compound of the desiredconcentration.

After the specified periods of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, for example, the compounds according to PreparationExamples I-2-b-2,1-2-b-1, I-1-b-2 and I-4-b-1 caused a destruction of atleast 98% after 13 days at an active compound concentration of, forexample, 0.1%.

Example G

Pre-Emergence Test

-   -   Solvent: 5 parts by weight of acetone    -   Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive.

After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control.

The figures denote:

-   -   0%=no action (like untreated control)    -   100%=total destruction

In this test, for example, the compound according to Preparation ExampleI-4-a-3 caused damage of 90% to Alopecurus myosuroids, 96% to Avenafatua and 95% to Setaria viridis when applied in an amount of, forexample, 500 g/ha, coupled with good tolerance by Beta vulgaris.

Example H

Test with Fly Larvae/Development-Inhibiting Action

-   -   Test animals: All larval stages of Lucilia cuprina        (OP-resistant) [pupae and adults (without contact with the        active compound)]    -   Solvent: 35 parts by weight of ethylene glycol monomethyl ether        35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, 3 parts by weight of active compoundare mixed with seven parts of the abovementioned solvent/emulsifiermixture and the emulsion concentrate thus obtained is diluted with waterto the particular desired concentration.

30 to 50 larvae per concentration are introduced onto horse-meat (1cm³), in glass tubes, onto which 500 μl of the dilution to be tested arepipetted. The glass tubes are placed in plastic beakers, the base ofwhich is covered with beach sand, and are stored in a climaticallycontrolled room (26° C.±1.5° C., 70% relative humidity±10%). The actionis checked after 24 hours and 48 hours (larvicidal action). Afteremergence of the larvae (about 72 hours), the glass tubes are removedand perforated plastic lids are placed on the beakers. After 1½ timesthe development period (hatching of the control flies), the flies whichhave hatched and the pupae/pupae cases are counted.

The criterion for the action is the onset of death among the treatedlarvae after 48 hours (larvicidal effect) or the inhibition of hatchingof adults from the pupae or the inhibition of pupae formation. Thecriterion for the in vitro action of a substance is the inhibition offlea development or a halt in development before the adult stage. 100%larvicidal action means that all the larvae have died after 48 hours.100% development-inhibiting action means that no adult flies havehatched.

In this test, for example, the compound according to Preparation ExampleI-4-a-1 caused an action of 100% at an active compound concentration of,for example, 1000 ppm.

Example I

Test with Boophilus microplus Resistant/SP-resistant Parkhurst Strain

-   -   Test animals: Adult satiated females    -   Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide,and lower concentrations are prepared by dilution in the same solvent.

The test is carried out as a 5-fold determination. 1 μl of the solutionsis injected into the abdomen and the animals are transferred to dishesand kept in a climatically controlled room. The action is determined viathe inhibition of oviposition. 100% means that no tick has laid.

In this test, for example, the compounds according to PreparationExamples I-4-a-1 and I-4-b-1 had an action of 100% at an active compoundconcentration of, for example, 20 μg per animal.

1. A compound of the formula (I)

in which X represents halogen, C₁-C₆-alkyl, C₂-C₆-alkenyl,C₂-C₆-alkinyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy,cyano or nitro, Y represents hydrogen, halogen, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, cyano or nitro,Z represents halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, hydroxyl, cyano, nitro, or phenoxy, phenylthio,thiazolyloxy, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy,phenyl-C₁-C₄-alkoxy or phenyl-C₁-C₄-alkylthio which are in each caseoptionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, nitro or cyano, Hetrepresents

A, B and the carbon atom to which they are bonded representC₃-C₁₀-cycloalkyl or C₅-C₁₀-cycloalkenyl, wherein one methylene group isoptionally replaced by oxygen or sulphur and which are optionallysubstituted by C₁-C₈-alkyl, C₃-C₁₀-cycloalkyl, C₁-C₈-halogenoalkyl,C₁-C₈-alkoxy, C₁-C₈-alkylthio, halogen or phenyl, or A, B and the carbonatom to which they are bonded represent C₅-C₆-cycloalkyl which issubstituted by an alkylenediyl group which optionally contains one ortwo oxygen and/or sulphur atoms or by an alkanedioxy group or by analkylenedithioyl group, this substituent forming a further five- toeight-membered ring with the carbon atom to which it is bonded, or A, Band the carbon atom to which they are bonded represent C₃-C₈-cycloalkylor C₅-C₈-cycloalkenyl in which two substituents, together with thecarbon atom to which they are bonded, represent C₃-C₆-alkanediyl,C₃-C₆-alkenediyl or C₄-C₆-alkylenediyl which are in each case optionallysubstituted by C₁-C₆-alkyl, C₁-C₆-alkoxy or halogen and wherein in eachcase one methylene group is optionally replaced by oxygen or sulfur, Grepresents hydrogen (a), or represents one of the groups

 wherein E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₁-C₈-alkyl,C₁-C₈-alkylthio-C₁-C₈-alkyl or poly-C₁-C₈-alkoxy-C₁-C₈-alkyl which arein each case optionally substituted by halogen, or representsC₃-C₈-cycloalkyl which is optionally substituted by halogen, C₁-C₆-alkylor C₁-C₆-alkoxy and in which one or two methylene groups are optionallyreplaced by oxygen and/or sulphur, or represents phenyl which isoptionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl, C₁-C₆-halogenoalkoxy, C₁-C₆-alkylthioor C₁-C₆-alkylsulphonyl, or represents phenyl-C₁-C₆-alkyl which isoptionally substituted by halogen, nitro, cyano, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl or C₁-C₆-halogenoxalkoxy, orrepresents 5- or 6- membered heteroaryl having one or two heteroatomsfrom the series consisting of oxygen, sulphur and nitrogen which isoptionally substituted by halogen or C₁-C₆-alkyl or representsphenoxy-C₁-C₆-alkyl which is optionally substituted by halogen orC₁-C₆-alkyl or represents 5- or 6-membered hetaryloxy-C₁-C₆-alkyl whichhas one or two heteroatoms from the series consisting of oxygen, sulphurand nitrogen and is optionally substituted by halogen, amino orC₁-C₆-alkyl, R² represents C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₈-alkoxy-C₂-C₈-alkyl or poly-C₁-C₈-alkoxy-C₂-C₈-alkyl which are ineach case optionally substituted by halogen, or representsC₃-C₈-cycloalkyl which is optionally substituted by halogen, C₁-C₆-alkylor C₁-C₆-alkoxy, or represents phenyl or benzyl which are in each caseoptionally substituted by halogen, cyano, nitro, C₁-C₆-alkyl,C₁-C₆-alkoxy, C₁-C₆-halogenoalkyl or C₁-C₆-halogenoalkoxy, R³ representsC₁-C₈-alkyl which is optionally substituted by halogen, or phenyl orbenzyl which are in each case optionally substituted by halogen,C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy,cyano or nitro, R⁴ and R⁵ independently of one another representC₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino, di-(C₁-C₈-alkyl)amino,C₁-C₈-alkylthio or C₃-C₈-alkenylthio which are in each case optionallysubstituted by halogen, or represent phenyl, phenoxy or phenylthio whichare in each case optionally substituted by halogen, nitro, cyano,C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio,C₁-C₄-halogenoalkylthio, C₁-C₄-alkyl or C₁-C₄-halogenoalkyl, R⁶ and R⁷independently of one another represent hydrogen, or representC₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₁-C₈-alkoxy, C₃-C₈-alkenyl orC₁-C₈-alkoxy-C₂-C₈-alkyl which are in each case optionally substitutedby halogen, or represent phenyl or benzyl which are in each caseoptionally substituted by halogen, C₁-C₈-alkyl, C₁-C₈-halogenoalkyl orC₁-C₈-alkoxy, or together represent a C₃-C₆-alkylene radical which isoptionally substituted by C₁-C₆-alkyl and in which one methylene groupis optionally replaced by oxygen or sulphur.
 2. A compound of theformula (I) according to claim 1, which X represents fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, cyano or nitro, Y represents hydrogen, fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, cyano or nitro, Z represents fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, hydroxy, cyano or nitro, or phenoxy or benzyloxywhich are in each case optionally substituted by fluorine, chlorine,bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₂-halogenoalkyl,C₁-C₂-halogenoalkoxy, nitro or cyano, Het represent

A, B and the carbon atom to which they are bonded representC₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, wherein in each case onemethylene group is optionally replaced by oxygen or sulphur and whichare optionally substituted by C₁-C₆-alkyl, C₃-C₈-cycloalkyl,C₁-C₃-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-alkylthio, fluorine, chlorineor phenyl, or A, B and the carbon atom to which they are bondedrepresent C₅-C₆-cycloalkyl which is substituted by an alkylenediyl groupwhich optionally contains one or two oxygen and/or sulphur atoms or byan alkylenedioxy group or by an alkylenedithioyl group, this substituentforming a further five- to seven-membered ring with the carbon atom towhich it is bonded, or A, B and the carbon atom to which they are bondedrepresent C₃-C₆-cycloalkyl or C₅-C₆-cycloalkenyl in which twosubstituents, together with the carbon atom to which they are bonded,represent C₃-C₅-alkanediyl, C₃-C₅-alkenediyl or butadienediyl which arein each case optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy,fluorine, chlorine or bromine, wherein in each case one methylene groupis optionally replaced by oxygen or sulfur, G represents hydrogen (a),or represents one of the groups

wherein E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents C₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₁-C₆-alkyl,C₁-C₆-alkylthio-C₁-C₆-alkyl or poly-C₁-C₆-alkoxy-C₁-C₆-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₇-cycloalkyl which is optionally substituted by fluorine,chlorine, C₁-C₅-alkyl or C₁-C₅-alkoxy and in which one or two methylenegroups are optionally replaced by oxygen and/or sulphur, or representsphenyl which is optionally substituted by fluorine, chlorine, bromine,cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio or C₁-C₄-alkylsulphonyl, orrepresents phenyl-C₁-C₄-alkyl which is optionally substituted byfluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₄-halogenoalkyl or C₁-C₄-halogenoxalkoxy, or represents pyrazolyl,thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl which are in each caseoptionally substituted by fluorine, chlorine, bromine or C₁-C₄-alkyl, orrepresents phenoxy-C₁-C₅-alkyl which is optionally substituted byfluorine, chlorine, bromine or C₁-C₄-alkyl or representspyridyloxy-C₁-C₅-alkyl, pyrimidyloxy-C₁-C₅-alkyl orthiazolyloxy-C₁-C₅-alkyl which are in each case optionally substitutedby fluorine, chlorine, bromine, amino or C₁-C₄-alkyl, R² representsC₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl orpoly-C₁-C₆-alkoxy-C₂-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₇-cycloalkylwhich is optionally substituted by fluorine, chlorine, C₁-C₄-alkyl orC₁-C₄-alkoxy, or represents phenyl or benzyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, cyano, nitro,C₁-C₄-alkyl, C₁-C₃-alkoxy, C₁-C₃-halogenoalkyl or C₁-C₃-halogenoalkoxy,R³ represents C₁-C₆-alkyl which is optionally substituted by fluorine orchlorine, or phenyl or benzyl which are in each case optionallysubstituted by fluorine, chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-alkoxy,C₁-C₂-halogenoalkyl, C₁-C₂-halogenoalkoxy, cyano or nitro, R⁴ and R⁵independently of one another represent C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₆-alkylamino, di-(C₁-C₆-alkyl)amino, C₁-C₆-alkylthio orC₃-C₄-alkenylthio which are in each case optionally substituted byfluorine or chlorine, or represent phenyl, phenoxy or phenylthio whichare in each case optionally substituted by fluorine, chlorine, bromine,nitro, cyano, C₁-C₃-alkoxy, C₁-C₃-halogenoalkoxy, C₁-C₃-alkylthio,C₁-C₃-halogenoalkylthio, C₁-C₃-alkyl or C₁-C₃-halogenoalkyl, R⁶ and R⁷independently of one another represent hydrogen, or representC₁-C₆-alkyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₃-C₆-alkenyl orC₁-C₆-alkoxy-C₂-C₆-alkyl which are in each case optionally substitutedby fluorine or chlorine, or represent phenyl or benzyl which are in eachcase optionally substituted by fluorine, chlorine, bromine, C₁-C₅-alkyl,C₁-C₅-halogenoalkyl or C₁-C₅-alkoxy, or together represent aC₃-C₆-alkylene radical which is optionally substituted by C₁-C₄-alkyland in which one methylene group is optionally replaced by oxygen orsulphur.
 3. A compound of the formula (I) according to claim 1, in whichX represents fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl,iso-butyl, isopropyl, tert-butyl, methoxy, ethoxy, propoxy, iso-propoxy,trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyano or nitro, Yrepresents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl,iso-propyl, butyl, iso-butyl, tert-butyl, methoxy, ethoxy, propoxy,iso-propoxy, trifluoromethyl, trifluoromethoxy, difluoromethoxy, cyanoor nitro, Z represents fluorine, chlorine, bromine, methyl, ethyl,propyl, butyl, iso-butyl, isopropyl, tert-butyl, methoxy, ethoxy,propoxy, iso-propoxy, trifluoromethyl, trifluoromethoxy,difluoromethoxy, cyano or nitro, Het represents

A, B and the carbon atom to which they are bonded representC₃-C₈-cycloalkyl or C₅-C₈-cycloalkenyl, wherein in each case onemethylene group is optionally replaced by oxygen or sulphur and whichare optionally substituted by methyl, ethyl, n-propyl, iso-propyl,butyl, iso-butyl, sec-butyl, tert-butyl, cyclohexyl, trifluoromethyl,methoxy, ethoxy, n-propoxy, iso-propoxy, butoxy, iso-butoxy, sec-butoxy,tert-butoxy, methylthio, ethylthio, fluorine, chlorine or phenyl, or A,B and the carbon atom to which they are bonded representC₅-C₆-cycloalkyl which is substituted by an alkylenediyl group whichoptionally contains one or two oxygen and/or sulphur atoms or by analkylenedioxy group, this substituent forming a further five- tosix-membered ring with the carbon atom to which it is bonded, or A, Band the carbon atom to which they are bonded represent C₃-C₆-cycloalkylor C₅-C₆-cycloalkenyl in which two substituents, together with thecarbon atom to which they are bonded, represent C₃-C₄-alkanediyl,C₃-C₄-alkenediyl or butadienediyl, wherein in each case one methylenegroup is optionally replaced by oxygen or sulfur, G represents hydrogen(a), or represents one of the groups

wherein E represents one metal ion equivalent or an ammonium ion, Lrepresents oxygen or sulphur, M represents oxygen or sulphur, R¹represents C₁-C₁₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,C₁-C₆-alkylthio-C₁-C₄-alkyl or poly-C₁-C₄-alkoxy-C₁-C₆-alkyl which arein each case optionally substituted by fluorine or chlorine, orrepresents C₃-C₆-cycloalkyl which is optionally substituted by fluorine,chlorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy and in which one ortwo methylene groups are optionally replaced by oxygen and/or sulphur,or represents phenyl which is optionally substituted by fluorine,chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl,methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, methylthio,ethylthio, methylsulfonyl or ethylsulfonyl, or represents benzyl whichis optionally substituted by fluorine, chlorine, bromine, methyl, ethyl,n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl ortrifluoromethoxy, or represents furanyl, thienyl or pyridyl which are ineach case optionally substituted by fluorine, chlorine, bromine, methylor ethyl, or represents phenoxy-C₁-C₄-alkyl which is optionallysubstituted by fluorine, chlorine, bromine, methyl or ethyl, orrepresents pyridyloxy-C₁-C₄-alkyl, pyrimidyloxy-C₁-C₄-alkyl orthiazolyloxy-C₁-C₄-alkyl which are in each case optionally substitutedby fluorine, chlorine, bromine, amino, methyl or ethyl, R² representsC₁-C₄-alkyl, C₂-C₁₄-alkenyl, C₁-C₄-alkoxy-C₂-C₆-alkyl orpoly-C₁-C₄-alkoxy-C₂-C₆-alkyl which are in each case optionallysubstituted by fluorine or chlorine, or represents C₃-C₆-cycloalkylwhich is optionally substituted by fluorine, chlorine, methyl, ethyl,n-propyl, iso-propyl or methoxy, or represents phenyl or benzyl whichare in each case optionally substituted by fluorine, chlorine, bromine,cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy,trifluoromethyl or trifluoromethoxy, R³ represents methyl, ethyl,propyl, iso-propyl, butyl or tert-butyl which is optionally substitutedby fluorine or chlorine, or phenyl or benzyl which are in each caseoptionally substituted by fluorine, chlorine, bromine, methyl, ethyl,iso-propyl, tert-butyl, methoxy, ethoxy, iso-propoxy, trifluoromethyl,trifluoromethoxy, cyano or nitro, R⁴ and R⁵ independently of one anotherrepresent C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylamino,di-(C₁-C₄-alkyl)amino or C₁-C₄-alkylthio which are in each caseoptionally substituted by fluorine or chlorine, or represent phenyl,phenoxy or phenylthio which are in each case optionally substituted byfluorine, chlorine, bromine, nitro, cyano, methyl, methoxy,trifluoromethyl or trifluoromethoxy, R⁶ and R⁷ independently of oneanother represent hydrogen, or represent C₁-C₄-alkyl, C₃-C₆-cycloalkyl,C₁-C₄-alkoxy, C₃-C₄-alkenyl or C₁-C₄-alkoxy-C₁-C₄-alkyl which are ineach case optionally substituted by fluorine or chlorine, or representphenyl or benzyl which are in each case optionally substituted byfluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, ortogether represent a C₅-C₆-alkylene radical which is optionallysubstituted by methyl or ethyl and in which one methylene group isoptionally replaced by oxygen or sulphur.
 4. A process for thepreparation of a compound of the formula (I) according to claim 1,wherein to obtain (B) a compound of the formula (I-2-a)

in which A, B, X, Y and Z have the abovementioned meanings, a compoundof the formula (III)

in which A, B, X, Y, Z and R⁸ have the abovementioned meanings, aresubjected to intramolecular condensation in the presence of a diluentand in the presence of a base, and, optionally the compounds of formula(I-2-a) are then (F)α) reacted with an acid halide of the formula (VIII)

in which Hal represents halogen, or β) reacted with a carboxylic acidanhydride of the formula (IX)R¹—CO—O—CO—R¹  (IX) in which R¹ has the abovementioned meaning,optionally in the presence of a diluent and optionally in the presenceof an acid-binding agent, or (G) reacted with chloroformic acid estersor chloroformic acid thioesters of the formula (X)R²—M—CO—Cl  (X) in which R² and M optionally in the presence of adiluent and optionally in the presence of an acid-binding agent, or(H)α) reacted with a chloromonothioformate acid ester orchlorodithioformic acid ester of the formula (XI)

in which M and R² have the abovementioned meanings, optionally in thepresence of a diluent and optionally in the presence of an acid-bindingagent, or β) reacted with carbon disulphide and then with compounds ofthe formula (XII)R²—Hal  (XII) in which R² has the abovementioned meaning and Halrepresents chlorine, bromine or iodine, optionally in the presence of adiluent and optionally in the presence of a base, or (I) reacted withsulphonic acid chlorides of the formula (XIII)R³—SO₂—Cl  (XIII) in which R³ optionally in the presence of a diluentand optionally in the presence of an acid-binding base, or (J) reactedwith phosphorus compounds of the formula (XIV)

in which L, R⁴ and R⁵ have the abovementioned meanings and Halrepresents halogen, optionally in the presence of a diluent and in thepresence of an acid-binding base, or (K) reacted with a metal compoundor amine of the formula (XV) or (XVI)Me(OR¹⁰)_(t)  (XV)

in which Me represents a mono- or divalent metal, t represents thenumber 1or 2 and R¹⁰, R¹¹ and R¹² independently of one another representhydrogen or alkyl, optionally in the presence of a diluent, or (L)α)reacted with isocyanoates or isothiocyanates of the formula (XVII)R⁶—N═C═L  (XVII) in which R⁶ and L optionally in the presence of adiluent and optionally in the presence of a catalyst, or β) reacted withcarbamic acid chlorides or thiocarbamic acid chlorides of the formula(XVIII)

in which L, R⁶ and R⁷ have the abovementioned meanings, optionally inthe presence of a diluent and optionally in the presence of anacid-binding agent.
 5. A pesticidal or herbicidal composition comprisinga pesticidally or herbicidally effective amount of a compound accordingto claim 1 and an extender.
 6. Process for the preparation of pestcontrol compositions and herbicides, characterized in that compounds ofthe formula (I) according to claim 1 are mixed with extenders and/orsurface-active agents.
 7. A method of combatting unwanted pests orvegetation which comprises administering to such pests or vegetation orto a locus from which it is desired to exclude such pests or vegetationa pesticidally or herbicidally effective amount of a compound accordingto claim 1.